WO2006136817A1 - Électrofilage de fibres - Google Patents

Électrofilage de fibres Download PDF

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Publication number
WO2006136817A1
WO2006136817A1 PCT/GB2006/002268 GB2006002268W WO2006136817A1 WO 2006136817 A1 WO2006136817 A1 WO 2006136817A1 GB 2006002268 W GB2006002268 W GB 2006002268W WO 2006136817 A1 WO2006136817 A1 WO 2006136817A1
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WO
WIPO (PCT)
Prior art keywords
orifice
jet
fibres
stream
poly
Prior art date
Application number
PCT/GB2006/002268
Other languages
English (en)
Inventor
Anthony John Ryan
David Norton
Original Assignee
The University Of Sheffield
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 The University Of Sheffield filed Critical The University Of Sheffield
Publication of WO2006136817A1 publication Critical patent/WO2006136817A1/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
    • D01D5/0061—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

Definitions

  • This invention relates to the electrospinning of fibres, and more particularly to a method for the electrospinning of axially aligned fibres, especially axially aligned nanofibres, and to axially aligned arrays thereof.
  • Patents describing various methods for the production of non woven fibres by electrospinning include: US 2003/0017208, US 5522879, US 5376117, US 4904272, US 4842505, US 4657793, US 4323525, US 4230650, US 4127706, US 4069026, US 4044404, US 4043331 , US 3994258 and US 1975504.
  • US 5024789 and US 4965110 describe an electrospinning method for producing tubular fibrous structures wherein the fibres are collected on an electrostatically charged mandrel, wherein the fibres take different paths from the source to the mandrel to produce a structure of smaller diameter fibres randomly oriented, larger diameter fibres and/or bundles of fibres circumferentially oriented and elongated voids circumferentially oriented.
  • US 4552707 describes a synthetic vascular graft made by electrospinning an organic polymeric material or a precursor thereof and collecting the spun fibres on a rotating mandrel, and controlling the speed of rotation of the mandrel such that a desired degree of anisotropy is present in the synthetic vascular graft.
  • US 4689186 describes the preparation of products having a tubular portion comprising electrospinning a fibre-forming liquid, the electrostatic field being distorted by the presence of an auxiliary electrode, preferably so as to encourage the deposition of circumferential fibres.
  • US 6592623 describes a muscle implant including an extracellular matrix made from electrospun polymer fibres.
  • the fibres can be formed from collagen and can be oriented in a specific direction, layered, or programmed to be completely random and unoriented.
  • the present invention provides an improved method for the production of highly aligned fibres by electrospinning wherein the fibres are collected whilst traveling in a focused electrostatic field.
  • the present invention provides a method for the production of an array of aligned fibres by electrospinning, which comprises forming a focused electrostatic field between a body having an orifice, maintained at a first electric potential, and a counter electrode, maintained at a second electric potential, the modulus of said second electric potential being greater than the modulus of said first electric potential, introducing a solution of a polymer in a volatile solvent into the electrostatic field through the orifice such that the polymer solution flows from the orifice towards the counter electrode in the form of a charged jet or stream, said jet or stream having a path length at least a portion of which is substantially straight, disposing a collector means in the path of the jet or stream at a position within the substantially straight portion thereof at which the solvent has evaporated sufficiently for the jet or stream to solidify, and moving the collector means relative to the jet or stream to deposit aligned fibres on the collector means.
  • the present invention provides an electrospinning apparatus for the production of an array of aligned fibres, which comprises a body having an orifice, means for maintaining the body at a first electric potential, a counter electrode disposed at a distance from the orifice, means for maintaining the counter electrode at a second electric potential, the modulus of said second electric potential being greater than the modulus of said first electric potential, means for introducing a solution of polymer in a volatile solvent through the orifice into a focused electrostatic field formed in the gap between the orifice and the counter electrode, such that the polymer solution flows from the orifice towards the counter electrode in the form of a charged jet or stream, said jet or stream having a path length at least a portion of which is substantially straight, and a collector means disposed in the path of the jet or stream at a position within the substantially straight portion thereof at which, in use, the solvent has evaporated sufficiently for the jet or stream to solidify, and means for moving the collector means relative to the jet or stream to deposit aligned fibres
  • the invention provides an array of aligned fibres produced by the method and/or apparatus of the invention.
  • an array of aligned fibres in this specification is meant a structure in which two or more fibres are oriented in a substantially parallel direction over at least a substantial part of their length.
  • the array of aligned fibres can have more than 10, more than 100, or more than 1000 fibres oriented in a substantially parallel direction over at least a substantial part of their length.
  • the fibres are oriented in a substantially parallel direction over substantially their entire length.
  • the fibres can be produced to any desired length, for example, more than 1 mm, more than 10 mm, more than 100 mm, or more than 1000 mm.
  • fibre diameters can also be produced using a method according to the invention, although the method of the invention can be especially useful for producing very small diameter fibres in the nanometre range.
  • fibre diameters of from 50 nm to 100 ⁇ m, preferably from 50 nm to 50 ⁇ m, more preferably from 100 nm to 1000 nm, for example, around 400 to 500 nm may be produced using a method of the invention.
  • fibres are formed from a solution or melt by streaming an electrically charged polymer solution or melt through an orifice.
  • the aligned fibres of the present invention comprise high molecular weight polymeric materials. These polymers, by virtue of their high molecular weight, form viscous solutions which can produce fibres, especially nanofibres, when subjected to an electrostatic potential. Polymers having molecular weights in the range of from 2000 g mol "1 to 5 million g mol "1 , preferably fromi OOOO g mol "1 to 2 million g mol '1 , more preferably from 50000 g mol "1 to 1 million g mol "1 can be used.
  • Suitable general purpose high molecular weight polymers useful in the present invention include both synthetic and natural fibre forming polymers, for example, cellulose acetate, polystyrene, PVA, PEO, PVP, polyacrylamide, polyurethane, polycarbonate, PTFE, PE, PP, polyacrylate, Kevlar, PHB, polyaniline, poly (phenylene terephthalamide) and silk.
  • Block copolymers and other thermoplastic elastomers are also useful in the present invention, for example, triblock copolymers comprising polystyrene, polybutadiene, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, such as the Kraton family (SBS, SIS, SEBS), and multi-block copolymers such as polyester-ethers, polyether-urethanes and polyether-ureas.
  • triblock copolymers comprising polystyrene, polybutadiene, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, such as the Kraton family (SBS, SIS, SEBS), and multi-block copolymers such as polyester-ethers, polyether-urethanes and polyether-ureas.
  • suitable polymers include, poly(ethylene oxide), polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone, hyaluronic acid, alginates, carragenen, cellulose derivatives such as carboxymethyl cellulose sodium, methyl cellulose, ethylcellulose, hydroxyethyl cellulose, hydroxypropylcellulose, hydroxypropylmethyl cellulose, hydroxypropylmethyl cellulose phthalate, cellulose acetate phthalate, noncrystalline cellulose, starch and its derivatives such as hydroxyethyl starch, sodium starch glycolate, chitosan and its derivatives, albumen, gelatin, collagen, polyacrylates and their derivatives, poly(alpha-hydroxy acids) and their copolymers such poly(caprolactone), poly(lactide-co-glycolide), poly(alpha- aminoacids) and their copolymers, poly(orthoesters), poly(ethylene oxide), polyvinyl alcohol, polyvinyl a
  • the aligned fibres are preferably water-soluble.
  • Water soluble polymers include but are not limited to, poly(ethylene oxide), polyvinyl alcohol, polyvinyl pyrrolidone, hyaluronic acid, alginates, carragenen, cellulose derivatives such as carboxymethyl cellulose sodium, hydroxyethyl cellulose, hydroxypropylcellulose, hydroxypropylmethyl cellulose, hydroxypropylmethyl cellulose phthalate, cellulose acetate phthalate, starch and its derivatives such as hydroxyethyl starch, sodium starch glycolate, dextrin, chitosan and its derivatives, albumen, zein, gelatin, and collagen.
  • DNA, RNA and other naturally occurring polymeric materials comprising nucleic acids and polypeptides can also be used in the method of the invention.
  • Water insoluble polymers useful in pharmaceutical applications include but are not limited to, polyvinyl acetate, methyl cellulose, ethylcellulose, noncrystalline cellulose, polyacrylates and their derivatives, poly(alpha- hydroxy acids) and their copolymers such as poly( ⁇ -caprolactone), poly(lactide-co-glycolid- e), poly(alpha-aminoacids) and their copolymers, poly(orthoesters), polyphosphazenes, poly(phosphoesters), and polyanhydrides.
  • Suitable volatile solvents for use herein include, but are not limited to, water, acetic acid, acetone, acetonitrile, methanol, ethanol, propanol, ethyl acetate,. propyl acetate, butyl acetate, butanol, N 1 N dimethyl acetamide, N, N dimethyl formamide, 1-methyl-2-pyrrolidone, dimethyl sulfoxide, diethyl ether, disisopropyl ether, tetrahydrofuran, pentane, hexane, 2-methoxyethanol, formamide, formic acid, hexane, heptane, ethylene glycol, dioxane, 2- ethoxyethanol, trifluoroacetic acid, methyl isopropyl ketone, methyl ethyl ketone, dimethoxy propane, methylene chloride , or mixtures thereof.
  • Preferred solvents include dichloromethane, chloroform, tetrahydrofuran and N 1 N dimethylformamide.
  • the solvent to polymer ratio is determined by the desired viscosity of the resulting solution.
  • the viscosity of the solution is within the range of from 1.5 to 50000 cp, more preferably from 50 tolOOOO cp, especially from 100 to 5000 cp.
  • the surface tension of the polymer solution is within the range of from 70 to 500 mNm "1 , and its electrical conductivity is within the range of from 1 to 300 Son 2 mol "1 .
  • a focused electrostatic field in this specification is meant an electrostatic field wherein the electric lines of force are relatively close together and divergence is kept to a minimum.
  • the body having the orifice is maintained at ground potential and the counter electrode is a point source upon which the electrostatic field is focused.
  • modulus of the electric potential means the magnitude of the electric potential, whether the charge is positive or negative.
  • the counter electrode can, for example, be a pin or pointed conductive rod, which can be connected to a high-voltage generator.
  • the potential difference between the body having the orifice and the counter electrode is preferably at least 1000V.
  • the pin or pointed rod is maintained at an electric potential of from 1000 to 50000 V, more preferably from 5000 to 30000 V, most preferably from 15000 to 25000 V.
  • the jet or stream issuing from the orifice can be kept substantially straight over a path length of several centimetres, for example, from 1 to 70 cms, preferably from 10 to 70 cms, or more, without significant jet whipping.
  • the term "orifice" means an opening or hole in a body through which the polymer solution can flow.
  • the body will be a hollow body, for example, a spinneret, or a hollow needle.
  • the body is formed from a conductive material, for example, a metal, and is preferably a capillary orifice, for example, a capillary needle.
  • Polymer sOlution can be supplied to the orifice from a reservoir by any suitable means, for example, by a pump or plunger mechanism that forces the polymer solution through the hollow body towards the orifice.
  • the polymer solution exits the orifice it flows in the form of a jet or stream, under the influence of the electrostatic field, in the direction of the counter electrode.
  • the path length of the polymer solution is substantially straight with relatively little jet whipping or splaying, at least in the portion of the path length adjacent to the orifice.
  • the solvent evaporates and the viscosity of the solution increases to a point at which the jet or stream can maintain its structural integrity.
  • the jet or stream is capable of maintaining its structural integrity, and is preferably self-supporting, it is considered to be "solidified" in the context of the present specification.
  • the collector means is disposed in the path of the jet or stream at a position such that the jet or stream is substantially straight and has lost sufficient of the solvent by evaporation to be "solidified" as defined in this specification. It will be appreciated that, even though the jet or stream may form one or more fibres capable of maintaining their structural integrity, the fibres may still contain substantial amounts of solvent, which can continue to evaporate from the fibres after deposition on the collector means.
  • the collector means is disposed at a distance of from 1 to 60 cms, more preferably from 10 to 50 cms, from the orifice.
  • the collector means can comprise, for example, a hollow spindle, having an axis of rotation at 90° to the direction of the electrostatic field.
  • the spindle can have 2, 3, 4, 5, 6, 10 or more bars around its circumference for receiving the deposited fibres. Rotation of the spindle enables long fibres to be collected, extending around the complete circumference thereof.
  • the collector means is preferably formed from an insulating material, for example, a plastics material such as PET, and is preferably rotated about insulated axles in order that it should not substantially distort the electrostatic field.
  • collector means could be a grid provided with translation means for moving the grid back and forth across the electrostatic field.
  • the collector could also be shaped in the form of a desired object, for example, a nose, ear, or other anatomical structure.
  • Aligned fibres can be removed from the collector means by any suitable method, for example, by picking the fibres and rolling them onto a separate storage spindle or glass slide, or by lifting them off the collector means directly onto a substrate.
  • Figure 1 shows a perspective view of an apparatus for reverse polarity electrospinning
  • Figure 2 shows a perspective view of a first electrospinning apparatus in accordance with the invention:
  • Figure 3 shows a perspective view of a second electrospinning apparatus in accordance with the invention enclosed within an insulated enclosure:
  • Figure 4 shows a perspective view of the apparatus of Figure 3 showing aligned fibres collecting on the spindle:
  • Figure 5 shows a perspective view of a pair of spindles suitable for use in the present invention:
  • Figure 6 shows scanning electron micrographs of polymer fibres collected (A) without the insulated box; and (B) with the insulated box:
  • Figure 7 shows light microscope pictures of block copolymer fibres formed using the apparatus of Figure 3 at a collector speed > 100 rpm:
  • Figure 8 shows (A) a scanning electron micrograph of a polylactide polymer spun by a conventional electrospinning method; and (B) a light microscope image of a polylactide polymer spun using the apparatus of Figure 3.
  • an electrospinning apparatus illustrated generally at 1 , comprising a syringe 2 having a reservoir 3 and a capillary needle 4.
  • the syringe 2 is mounted upon a pump 5.
  • the needle 4 is maintained at ground potential by a connecting ground wire 6.
  • the needle 4 is demountable and can be replaced by other capillary needles having a range of diameters depending upon the viscosity of the polymer solution used and the desired fibre diameter.
  • the counter electrode comprises a second needle 7, which is aligned with the capillary needle 4, and connected to a high-voltage DC source 8 by a wire 9.
  • a jet 10 of polymer solution is ejected through the capillary needle 4.
  • the path length of the jet 10 is straight for a distance D until it reaches the point 11 , at which it becomes charged and is repelled from the counter electrode needle 7. It has been found that the distance D is greater for less polar solvents and is also increased by increasing the gap between the capillary needle 4 and the counter electrode needle 7, and by increasing the applied voltage.
  • the collector 12 interposed between the capillary needle 4 and the counter electrode needle 7.
  • the collector 12 comprises a rotatable spindle 13, having insulated axles 14, and provided with a series of bars 15, arranged around its circumference.
  • the spindle 13 is rotated by means of a high-speed electric motor 16.
  • the collector 12 is positioned such that the jet 10 passes through it whilst still straight. Rotation of the spindle enables aligned, oriented fibres to be collected on the bars 15.
  • the orientation of the fibres can be increased by increasing the rotation speed of the spindle 13 up to the point at which the circumferential velocity of the spindle exceeds the velocity of the jet 10.
  • Figure 3 illustrates a modified apparatus which is suitable for polymer solutions in less volatile or more polar solvents.
  • the path length of the jet should be as long as possible in order to allow for sufficient evaporation of the solvent and drying of the fibres.
  • the modified apparatus is similar to that shown in Figure 2, except that the capillary needle 4, the collector 12 and the counter electrode 7 are enclosed in a semi-insulated enclosure 17. This increases the distance D by shielding the charged jet of polymer solution from earth points.
  • Figure 4 shows the apparatus of Figure 3 with a series of aligned fibres 18 collected on the bars 15 of the spindle 13.
  • Figure 5 shows two designs of spindle suitable for use in the apparatus of the present invention.
  • the three-bar spindle 19 is suitable for a broad range of polymers and fibres, but polymers which form brittle fibres or fibres of very small diameter ( ⁇ 1 ⁇ m) may be broken as they are stretched over the spindle. In such cases, a spindle with more bars can be used in order that the gap over which the fibres are unsupported is decreased.
  • the six-bar spindle 20 can overcome this problem.
  • Figure 6 (A) shows a scanning electron micrograph of polymer fibres collected using the apparatus of Figure 2, that is to say, without the semi-insulated enclosure, using a counter electrode voltage of 20 kV and a collector rotation speed of 300 rpm.
  • Figure 6 (B) shows a scanning electron micrograph of fibres of the same polymer collected using the apparatus of Figure 3, using a counter electrode voltage of 20 kV and a collector rotation speed of 300 rpm. It can be seen that the fibres of Figure 6 (B) are of smaller diameter, and form a more dense aligned array.
  • Figure 7 shows light microscope pictures of a block copolymer electrospun using the apparatus of Figure 3.
  • the counter electrode voltage was 17.5 kV and the collector speed of rotation was >100 rpm.
  • Figure 8 (A) shows a scanning electron micrograph of a polylactide polymer spun using a conventional electrospinning technique with a charged orifice and a grounded rotating mandrel collector.
  • Figure 8 (B) shows a light microscope image of the same polymer spun using the apparatus of Figure 3, using an orifice at ground potential and a counter electrode voltage of 22.5 kV. It can be seen that the fibres of Figure 8 (B) are of smaller diameter, are more highly aligned and more densely deposited than the fibres of Figure 8 (A).

Abstract

La présente invention concerne un procédé destiné à la production d'un tableau de fibres alignées par électrofilage, qui passe par la formation d'un champ électrostatique ciblé entre un corps possédant un orifice, maintenu à un premier potentiel électrique, et une contre-électrode, maintenue à un second potentiel électrique ; le module du second potentiel électrique est supérieur au module du premier potentiel électrique, ce qui introduit une solution d'un polymère dans un solvant volatil dans le champ électrostatique via l'orifice, de sorte que la solution de polymère passe de l'orifice à travers la contre-électrode sous la forme d'un jet ou d'un flux chargé, ledit flux ou jet possède une longueur de chemin dont au moins une partie est sensiblement droite. Un moyen de collecte est déposé dans le chemin du jet ou du flux à une place située dans sa partie sensiblement droite où le solvant s'est suffisamment évaporé pour que le jet ou le flux se solidifie et le moyen de collecte est déplacé par rapport au jet ou au flux pour déposer des fibres alignées sur le moyen de collecte.
PCT/GB2006/002268 2005-06-21 2006-06-20 Électrofilage de fibres WO2006136817A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0512629.7 2005-06-21
GB0512629A GB2427382A (en) 2005-06-21 2005-06-21 Electrospinning of fibres

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WO2008150970A2 (fr) * 2007-05-30 2008-12-11 Dow Global Technologies Inc. Électrofilature à base de solvant à haut rendement
WO2012084427A1 (fr) 2010-12-22 2012-06-28 Unilever Nv Compositions comprenant une phase liquide non aqueuse structurée
WO2012084441A1 (fr) 2010-12-22 2012-06-28 Unilever Nv Compositions sous la forme de fibres
CN102776709A (zh) * 2012-07-10 2012-11-14 东华大学 静电纺丝制备聚乙烯吡咯烷酮/壳聚糖复合纳米纤维膜
WO2013000442A1 (fr) 2011-06-27 2013-01-03 Contipro Biotech S.R.O. Procédé de production de matériaux présentant des propriétés anisotropes et composés de nanofibres ou de microfibres, et appareil pour mettre en œuvre ledit procédé
EP2595695A2 (fr) * 2010-07-19 2013-05-29 Neograft Technologies Inc. Dispositifs de greffe et procédés d'utilisation
WO2013092024A1 (fr) 2011-12-21 2013-06-27 Unilever N.V. Compositions comprenant une phase grasse structurée
US8492332B2 (en) 2007-04-19 2013-07-23 Fibralign Corporation Oriented collagen-based materials, films and methods of making same
US8513382B2 (en) 2008-08-11 2013-08-20 Fibralign Corporation Biocomposites and methods of making the same
CN103334168A (zh) * 2013-07-24 2013-10-02 苏州大学 一种静电纺丝的接收装置
US20130317285A1 (en) * 2011-01-14 2013-11-28 Neograft Technologies, Inc. Apparatus for Creating Graft Devices
CN105177735A (zh) * 2015-10-27 2015-12-23 北京航空航天大学 一种制备三维有序组织工程支架的静电纺丝装置
CN105200540A (zh) * 2015-10-27 2015-12-30 北京航空航天大学 一种利用磁场诱导制备轴向有序排列管状物的静电纺丝装置
US9295541B2 (en) 2009-12-31 2016-03-29 Neograft Technologies, Inc. Graft devices and methods of fabrication
US9724308B2 (en) 2010-09-10 2017-08-08 Fibralign Corporation Biodegradable multilayer constructs
US10065046B2 (en) 2010-07-15 2018-09-04 Fibralign Corporation Conductive biopolymer implant for enhancing tissue repair and regeneration using electromagnetic fields
US10086079B2 (en) 2008-08-11 2018-10-02 Fibralign Corporation Biocomposites and methods of making the same
US10238769B2 (en) 2011-10-11 2019-03-26 Fibralign Corporation Graft for directed vascular and lymphatic regeneration and methods to guide endothelial cell assembly
CN111850837A (zh) * 2020-07-24 2020-10-30 吉林农业大学 玉米醇溶蛋白基单轴静电纺丝取向纤维膜及其制备方法
US11273235B2 (en) 2013-10-10 2022-03-15 Fibralign Corporation Method and device for lymphedema treatment

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US11236442B2 (en) 2013-03-14 2022-02-01 Lifenet Health Electrospinning apparatus and methods of use thereof
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JP6460815B2 (ja) * 2015-02-02 2019-01-30 キヤノン株式会社 光沢部材の製造方法
US10801131B2 (en) * 2016-05-24 2020-10-13 The Johns Hopkins University Electrospinning aramid nanofibers
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US8492332B2 (en) 2007-04-19 2013-07-23 Fibralign Corporation Oriented collagen-based materials, films and methods of making same
WO2008150970A3 (fr) * 2007-05-30 2009-04-16 Dow Global Technologies Inc Électrofilature à base de solvant à haut rendement
WO2008150970A2 (fr) * 2007-05-30 2008-12-11 Dow Global Technologies Inc. Électrofilature à base de solvant à haut rendement
US8584871B2 (en) 2007-05-30 2013-11-19 Dow Global Technologies Llc High-output solvent-based electrospinning
US10086079B2 (en) 2008-08-11 2018-10-02 Fibralign Corporation Biocomposites and methods of making the same
US8513382B2 (en) 2008-08-11 2013-08-20 Fibralign Corporation Biocomposites and methods of making the same
US9295541B2 (en) 2009-12-31 2016-03-29 Neograft Technologies, Inc. Graft devices and methods of fabrication
US10065046B2 (en) 2010-07-15 2018-09-04 Fibralign Corporation Conductive biopolymer implant for enhancing tissue repair and regeneration using electromagnetic fields
EP2595695A4 (fr) * 2010-07-19 2014-01-22 Neograft Technologies Inc Dispositifs de greffe et procédés d'utilisation
US9445874B2 (en) 2010-07-19 2016-09-20 Neograft Technologies, Inc. Graft devices and methods of use
US10239071B2 (en) 2010-07-19 2019-03-26 Neograft Technologies, Inc. Graft devices and methods of use
EP2595695A2 (fr) * 2010-07-19 2013-05-29 Neograft Technologies Inc. Dispositifs de greffe et procédés d'utilisation
US20140005470A1 (en) * 2010-07-19 2014-01-02 Neograft Technologies, Inc. Graft Devices and Methods of Use
US9724308B2 (en) 2010-09-10 2017-08-08 Fibralign Corporation Biodegradable multilayer constructs
WO2012084441A1 (fr) 2010-12-22 2012-06-28 Unilever Nv Compositions sous la forme de fibres
WO2012084427A1 (fr) 2010-12-22 2012-06-28 Unilever Nv Compositions comprenant une phase liquide non aqueuse structurée
US10085829B2 (en) * 2011-01-14 2018-10-02 Neograft Technologies, Inc. Apparatus for creating graft devices
US20130317285A1 (en) * 2011-01-14 2013-11-28 Neograft Technologies, Inc. Apparatus for Creating Graft Devices
CN103687984A (zh) * 2011-06-27 2014-03-26 康迪普罗生物技术公司 由纳米纤维或微米纤维组成的具有各向异性属性材料的生产方法及实施该方法的设备
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CN103334168A (zh) * 2013-07-24 2013-10-02 苏州大学 一种静电纺丝的接收装置
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