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WO2007013858A1 - Procédé et appareil de production de fil constitué de fibres - Google Patents

Procédé et appareil de production de fil constitué de fibres Download PDF

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Publication number
WO2007013858A1
WO2007013858A1 PCT/SG2006/000208 SG2006000208W WO2007013858A1 WO 2007013858 A1 WO2007013858 A1 WO 2007013858A1 SG 2006000208 W SG2006000208 W SG 2006000208W WO 2007013858 A1 WO2007013858 A1 WO 2007013858A1
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WO
WIPO (PCT)
Prior art keywords
solvent
fiber
receptacle
yarn
fiber yarn
Prior art date
Application number
PCT/SG2006/000208
Other languages
English (en)
Inventor
Wee Eong Teo
Kazutoshi Fujihara
Seeram Ramakrishna
Original Assignee
National University Of Singapore
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 National University Of Singapore filed Critical National University Of Singapore
Publication of WO2007013858A1 publication Critical patent/WO2007013858A1/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
    • D01D5/0046—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by coagulation, i.e. wet 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
    • D01D5/0092—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
    • D01D5/06—Wet spinning methods

Definitions

  • the present invention generally relates to the fabrication of electrospun fiber yarns and to apparatuses used in their manufacture.
  • Textile fabrics have been used in various industrial applications, such as protective cloth, sports wear and apparel cloths. They can be chemically functionalized to achieve desired properties such as higher hydrophobicity, higher moisture absorption, excellent draping, ease of stain removal, anti-microbial activity, etc. In order to enhance these functionalities, the fiber surface area to volume ratio has been increased by reducing the fiber diameter.
  • Electrospinning is a relatively easy and simple method to produce smaller diameter continuous fibers, that is, fibers of diameters in the nanometer to sub- micron size range.
  • a charge of about 5 to about 30 kV is applied by an electrode to a polymer solution.
  • the charged polymer solution is separated at a defined distance from a collector, which is also charged with an opposite polarity to the first electrode.
  • a static electric field is established between the charged polymer solution and the collector to thereby form a Taylor Cone therebetween.
  • the Taylor Cone forms due to the competing forces of the static electric field and the polymer solution's surface tension. Assuming that the concentration of the polymer in solution is sufficiently high to cause molecular chain entanglement, a fiber is drawn from the tip of the Taylor cone onto the collector.
  • the charged polymer solution is usually ejected from a nozzle of a spinneret to form a jet which is deposited onto the oppositely charged collector. While the jet travels from the nozzle to the collector, the solvent of the polymer solution evaporates so that a polymer fiber is left to accumulate on the collector. The charge on the fibers eventually dissipates into the surrounding environment.
  • the fibers may have a diameter between about 50 nanometers to about 10 microns.
  • a problem associated with known electrospinning techniques is that as the non-woven fibers are so small and fragile, it can often be very difficult to wind the yarn on a roll. This is particularly the case for electrospun yarns being produced on an industrial scale. There is a need to provide a method of producing electrospun fiber yarns that overcomes, or at least ameliorates, one or more of the disadvantages described above .
  • a method for producing a fiber yarn comprising the step of electrospinning a fiber into a non-solvent contained within a receptacle, the receptacle comprising an outlet conduit to allow non-solvent to flow therefrom, wherein the dimensions of the outlet conduit are such that as non- solvent flows therefrom, flow conditions of said non- solvent within said receptacle form said yarn.
  • the non-solvent provides a support for the electrospun fibers and thereby inhibits breakage of said fibers.
  • a method for producing a fiber yarn comprising the step of rotating a non-solvent about an axis as a fiber is electrospun from a charged polymer solution and dispensed into said rotating non-solvent to thereby form said fiber yarn.
  • the rotation of said fibers causes said fibers to twist and thereby form a yarn.
  • the rotation of said fibers during their formation within said non-solvent allows the formed yarn to be wound on a roller without becoming tangled.
  • a fiber yarn made in a method comprising the step of electrospinning a fiber into a non-solvent contained within a receptacle, the receptacle comprising an outlet conduit to allow non-solvent to flow therefrom, wherein the dimensions of the outlet conduit are such that as non- solvent flows therefrom, flow conditions of said non- solvent within said receptacle form said yarn.
  • a fiber yarn made in a method comprising the step of rotating a non-solvent about an axis as an electrospun fiber is dispensed into said rotating non-solvent to thereby produce said fiber yarn.
  • a fiber yarn manufacturing apparatus for making fiber yarn comprising: a non-solvent receptacle for containing non-solvent therein, said non-solvent being at least partially insoluble to a polymer solution; a nozzle disposed above the non-solvent for dispensing a jet of charged polymer solution into said non-solvent; and an outlet conduit extending from said receptacle to allow non-solvent to flow therefrom, wherein the dimensions of the outlet conduit are such that as non-solvent flows therefrom, flow conditions of said non-solvent within said receptacle form said yarn.
  • a fiber yarn manufacturing system comprising: a receptacle for containing non-solvent therein; and a rotator capable of rotating the non-solvent about an axis, wherein in use, a fiber is electrospun from a charged polymer solution and dispensed into said rotating non- solvent to produce said fiber yarn.
  • the following words and terms used herein shall have the meaning indicated:
  • the term "electrospun fiber yarn” is to be interpreted broadly to include any yarns that have been formed from fibers that had been electrospun. Such fibers may have diameters from the nanometer to the sub-micron scale.
  • the term "polymer solution” is to be interpreted broadly to include any solution comprising one or more polymer, copolymer or polymer blend dissolved in a solvent and which comprises a concentration of polymers that is capable of being electrospun.
  • Exemplary polymers include, but are not limited to, poly (vinylidenefluoride) , poly (vinylidene fluoride-co-hexafluoropropylene) , polyacrylonitrile, poly (acrylonitrile-co-methacrylate) , polymethylmethacrylate, polyvinylchloride, poly (vinylidenechloride-co-acrylate) , polyethylene, polypropylene, nylon series such as nylonl2 and nylon-4,6, aramid, polybenzimidazole, polyvinylalcohol, cellulose, cellulose acetate, cellulose acetate butylate, polyvinyl pyrrolidone-vinyl acetates, poly (bis- (2-methoxy- ethoxyethoxy) ) phosphazene (MEEP) , poly (ethylene imide) , poly (ethylene succinate), poly (ethylene sulphide), poly (oxymethylene-oligo-oxyethylene) , poly (propyleneoxid
  • non-solvent is to be interpreted broadly to include any liquids that, at least partially, do not dissolve the polymer of the fiber.
  • the non-solvent is water.
  • vortex-like manner is to be interpreted broadly to include a spiral motion of non-solvent within a receptacle, wherein spiral motion of the mass of the non- solvent tends to draw the non-solvent towards its center.
  • composite yarn is to be interpreted broadly to include any yarn that may be made from a mixture of polymer solutions.
  • the term "about”, in the context of concentrations of components of the formulations, typically means +/- 5% of the stated value, more typically +/- 4% of the stated value, more typically +/- 3% of the stated value, more typically, +/- 2% of the stated value, even more typically +/- 1% of the stated value, and even more typically +/- 0.5% of the stated value.
  • range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosed ranges. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 • to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.
  • Exemplary, non-limiting embodiments of a method of producing a fiber yarn comprising the step of electrospinning a fiber into a non-solvent contained within a receptacle, the receptacle comprising an outlet conduit to allow non-solvent to flow therefrom, wherein the dimensions of the outlet conduit are such that as non- solvent flows therefrom, flow conditions of said non- solvent within said receptacle form said yarn.
  • the dimensions of the outlet conduit may be such that it aids in the rotation of said non-solvent contained within said receptacle.
  • the rotating may be such that said non-solvent is caused to flow in a vortex-like manner.
  • the spiral motion of the non- solvent flowing in a vortex-like manner promotes twisting of the fiber and thereby assists in the formation of the yarn.
  • the method may comprise the step of removing said formed fiber yarn from said non-solvent. Removal of the fiber yarn from the non-solvent allows it to be wound on a roller.
  • the method may comprise the step of injecting multiple jets of said charged polymer solution into said rotating non-solvent to form multiple fibers.
  • the rotation of said non-solvent causes said formed multiple fibers to form a single fiber yarn.
  • multiple jets of different types of charged polymer solutions may be injected into said rotating non-solvent to form multiple fibers. These fibers may be twisted by the rotating non-solvent to form a single composite fiber yarn.
  • the method may comprise the step of injecting a jet of said charged polymer solution into said non-solvent, wherein said jet is projected from at least one spinneret selected from the group consisting of a uniaxial spinneret, a co-axial spinneret, a bi-capillary spinneret and a multi-capillary spinneret.
  • the method may comprise the step of using water as the non-solvent.
  • the method may comprise the step of applying an electrical ground to said non-solvent during electrospinning of said polymer solution.
  • the electrical ground provides an electrical pathway to dissipate the electric charge of the formed fiber present in the non- solvent .
  • the method may comprise the step of providing one or more additives in said non-solvent selected from the group consisting of sugars, amino acids, proteins, growth factors, vitamins, hormones, cytokines, coloring dye, binders and cells. These additives may therefore be adsorbed or encapsulated on the surface of the formed fibers to thereby enhance the functionality of the yarn.
  • the rotating fluid flow may be created by the step of allowing said rotating solvent to be removed from said receptacle.
  • the outlet conduit may be dimensioned such that as said non-solvent flows therefrom, said non-solvent flows in a vortex-like manner within said receptacle.
  • the outlet conduit has a diameter of about 5mm to about 20mm, about 10mm to about 20mm, about 15mm to about 20mm, about 5mm to about 10mm, about 5mm to about 15mm.
  • the height of the non-solvent above the outlet conduit is about 100 mm to about 200 mm, about 120 mm to about 200 mm, about 140 mm to about 200 mm, about 160 mm to about 200 mm, about 180 mm to about 200 mm, about 100 mm to about 180 mm, about 100 mm to about 160 mm, about 100 mm to about 140 mm, about 100 mm to about 120 mm.
  • the height of water as non- solvent in a receptacle above a 5 mm diameter outlet conduit having a diameter of 350 mm is maintained at a level between about 100 to about 200 mm to create the vortex.
  • the above disclosed embodiments are exemplary and that the creation of the vortex may be dependent on the viscosity of the non- solvent used, the head pressure of the non-solvent (ie the level of non-solvent above the outlet conduit) and possibly the shape and dimensions of the receptacle.
  • a mathematical model for the theoretical formation of a vortex of a non-compressible fluid is known in the art.
  • Transport Phenomena Bird et al, Chapter 3, John Wiley & Sons, 1960 provides a general discussion of vortex fluid flows and in particular pages 108-111 disclose a mathematical model for prediction of a vortex depth in an agitated tank.
  • Vortices in agitated tanks have also been experimentally investigated in other literature such as Memoirs of the Faculty of Engineering, Kyoto University, Vol. XVII, No. Ill, July 1955 by S Nagata et al. Although these are idealized fluid flow models they can function as an approximation of vortex fluid flow in a receptacle. The creation of a vortex may ultimately be verified empirically.
  • the rotating fluid flow may be created by the step of pumping non-solvent into a receptacle to cause said non-solvent to rotate therein.
  • said pump pumps non-solvent into said receptacle via a non-solvent inlet provided within said receptacle.
  • the dimension of said non-solvent inlet and the pressure exerted by said pump causes said non- solvent to flow in a vortex-like manner within said receptacle.
  • the non- solvent is pumped substantially tangential to the surface of the non-solvent at a speed selected from the group consisting of about 5 m/s to about 15 m/s, about 8 m/s to about 15 m/s, about 10 m/s to about 15 m/s, about 10 m/s to about 14 m/s, and about 11 m/s to about 13 m/s.
  • the method may comprise the step of providing a funnel disposed within said receptacle such that said formed fiber is emitted from the outlet conduit located in said receptacle via the spout of said funnel, wherein the funnel is dimensioned such that it promotes the creation of the vortex-like fluid flow within the receptacle.
  • the funnel outlet has a diameter of about 5mm to about 20mm, about 10mm to about 20mm, about 15mm to about 20mm, about 5mm to about 10mm, about 5mm to about 15mm.
  • the spout of the funnel acts as a guide to guide the formed yarn into the hole and thereby be ejected from the receptacle.
  • the charged polymer solution may be selected from the group consisting of polylactide, polycaprolactone, poly (glycolic acid), polyvinylidene fluoride, polyvinylidene fluoride-co-hexafluoropropylene, polyesters, polyamides, polyimides, polyethylenes, polyolefins, polypropylenes, poly (vinyl alcohols), polyacrylonitriles, polycarbamides, polyurethanes and mixtures thereof. Copolymers, polymer melts and blends of the above polymers may also be used.
  • the solution to be electrospun may be ceramic precursors.
  • the method may comprise the step of selecting the diameter of said fiber yarn by varying any one or more of the following: (i) the feedrate of said charged polymer solution into said non-solvent; (ii) the number of spinnerets used to inject said charged polymer solution into said non-solvent; (iii) the diameter of said charged polymer solution that is injected by a spinneret into the non-solvent; and (iv) the size of a hole provided in said receptacle containing said rotating non-solvent.
  • the fiber yarn may be at least one of a solid fiber yarn, hollow fiber yarn, tubular fiber yarn and a twisted fiber yarn.
  • the method may comprise the step of providing an auxiliary electrode to a jet of said polymer solution as it is electrospun into said non-solvent, wherein said auxiliary electrode distorts the electrostatic field of said jet of polymer solution to thereby cause it to rotate about an axis as it enters said non-solvent.
  • the use of the auxiliary electrodes controls the flight path of the charged electrospinning jet. It will be appreciated that the actual spinning jet may be unstable and therefore the "rotation" is not necessarily about a fixed axis.
  • the method may comprise the step of agitating the non-solvent in a receptacle to cause it to rotate about the axis .
  • the method may comprise the step of rotating a receptacle containing said non-solvent to cause said non- solvent to rotate about the axis.
  • Fig. 1 is a schematic diagram of a first disclosed apparatus for forming fiber yarn from electrospun fiber.
  • Fig. 2 is a schematic diagram of a second disclosed apparatus for forming fiber yarn from electrospun fiber.
  • Fig. 3 is a schematic diagram of multiple spinnerets being used to form a single fiber yarn in accordance with a disclosed embodiment.
  • Fig. 4A is an SEM image at 400Ox magnification of poly (vinylidene fluoride) electrospun fiber yarn formed in a method of the disclosed embodiment.
  • Fig. 4B is an SEM image at 300Ox magnification of a cross-sectional view of the fiber yarn of Fig. 4A.
  • Fig. 4C is an SEM image at 200Ox magnification of poly (caprolactone) electrospun fiber yarn formed in a method of the disclosed embodiment.
  • Fig. 4D is an SEM image at 300Ox magnification of a cross-sectional view of the fiber yarn of Fig. 4C.
  • Fig. 5 is an SEM image at 50Ox magnification of the twisted poly (caprolactone) fiber yarn formed in a method of the disclosed embodiment.
  • Fig. 6 is a photograph diagram of a tape-like electrospun fiber yarn drawn at a speed of 1 m/min without vortex in the non-solvent.
  • Fig. 7 is an SEM image at 80Ox magnification of a tape-like electrospun fiber yarn drawn at a speed of 1 m/min without vortex in the non-solvent.
  • Fig. 8 is a schematic diagram of a third disclosed apparatus for forming fiber yarn from electrospun fiber. Disclosure of Detailed Embodiment
  • Fig. 1 shows a schematic diagram of an apparatus 100 for forming a fiber yarn according to a disclosed embodiment.
  • the apparatus 100 comprises a non-solvent receptacle in the form of container 3 for containing non- solvent in the form of water which is insoluble to a charged polymer solution which is electrospun to form a fiber.
  • the container 3 is disposed about a vertical axis as shown by arrow 20.
  • non-solvent present in the container 3 is made to rotate in the direction of arrow 22 about the axis 20 to allow the non-solvent to flow in a vortex fluid flow 10 within the container 3.
  • the vortex fluid flow 10 twists the fibers which are electrospun into the non-solvent to thereby form a fiber yarn 14.
  • a spinneret 1 having a nozzle IA is disposed above the container 3 to electrospin a fiber into the non- solvent of the container 3.
  • Electrospinning is a known processes and is described in the literature, for example in Fong, H.; Reneker, D. H.; J. Polym. Sci., Part B, 37 (1999), 3488, and in US Patent Nos. 6,616,435, 6,713,011, 4,043,331, 4,878,908 and 6,790,528.
  • a high voltage 2 of about 5 to 50 kV is applied to the spinneret to charge the polymer solution contained therein. Electrospinning occurs as a jet 5 of the charged polymer solution is dispensed from the nozzle IA into the rotating non- solvent of the container 3.
  • the apparatus After dispensation of the jet 5 from the nozzle IA, the solvent of the charged polymer solution evaporates to thereby form a fiber which deposits as a fiber mesh 8 on the surface of the rotating non-solvent disposed within the container 3.
  • the apparatus also has an outlet conduit in the form of a hole 9 located in the bottom of the container 3. The hole is disposed on the axis 20 and is dimensioned such that a vortex fluid flow 10 is created within the container 3 as non-solvent is emitted from the hole 9 under gravity.
  • the high voltage 2 is also applied to a ring-shaped electrode 7 disposed between the spinneret 1 and top of the container 3 to thereby distort the electrostatic field surrounding the polymer jet 5 as it is emitted from the nozzle IA. Distortion of the electrostatic field surrounding the polymer jet 5 promotes rotation of the polymer jet 5 about the axis 20 within the electrostatic field defined by the ring-shaped electrode 7 as it forms fiber and enters the non-solvent.
  • the non-solvent is grounded to establish a static electric field between the spinneret 1 and container 3 and to thereby form a Taylor Cone therebetween.
  • the grounded non-solvent also allows for an electrical pathway to dissipate the electric charge of the formed fiber mesh 8 present in the non-solvent.
  • the fiber mesh 8 When the fiber mesh 8 is deposited on the surface of the non-solvent just before it is drawn into a hole 9 at the bottom of the container 3, other substances such as salt, nano-particles, cells, proteins, vitamins, sugar, etc, may be added on top of the fiber mesh 8 such that the substance gets encapsulated or mixed with the fibers as it is drawn into a fiber yarn 14. Other chemicals such as, but not limited to, sugars, amino acids, proteins, growth factors, vitamins, hormones, cytokines, coloring dye, binders may be added to the non-solvent such that the fiber yarn 14 is automatically coated during the drawing process.
  • the container 3 is cylindrical in shape but it will be appreciated that the container 3 can be of any shape.
  • the vortex fluid flow 10 is created in the non- solvent to facilitate formation of the fiber yarn 14 from the fiber mesh 8 that is deposited on the surface of the non-solvent.
  • the rotator in addition to the hole 9, also comprises pumping non-solvent under pressure into the container to thereby promote vortex fluid flow formation.
  • the rotator further comprises a liquid conduit 18 which is disposed adjacent to the surface of the container 3 to emit pressurized non-solvent which has been pumped by pump 11.
  • the pressurized non-solvent is tangentially introduced onto the surface of the non- solvent within container 3 in the rotating direction 22 of the vortex fluid flow 10.
  • the inlet of the pump 11 is connected to a non-solvent feed tank 13, disposed at the bottom of container 3, for feeding non-solvent into the container.
  • the speed of the vortex fluid flow 10 is controlled by the rate at which non-solvent is pumped into the container 3.
  • An opening 12 at the side of container 3 near the top is used to discharge any excess non-solvent to feed tank 13 so as to maintain the level of non-solvent in container 3. This excess non-solvent is recycled back to container 3 from feed tank 13 via pump 11 and liquid conduit 18.
  • the non-solvent that flows out through hole 9 flows into feed tank 13 and is recycled back to container 3 via pump 11 and liquid conduit 18.
  • the fiber yarn 14 is drawn from hole 9 located at the bottom of container 3. It is guided by a guide 19 to a roller 15. As the roller 15 rotates, it winds the drawn fiber yarn 14 onto it.
  • An example of a fiber yarn 14 formed according to this embodiment is seen from Figs. 4A and 4B.
  • the vortex fluid flow 10 causes the fiber to twist while it is resident in the container 3.
  • the twisting of the fiber produces a yarn 14.
  • Fig. 2 shows a schematic diagram of an apparatus 100' having a number of technical features that are the same as the apparatus 100 described above which are indicated by the same reference numeral but with a prime symbol (')•
  • the apparatus 100' does not have a ring electrode 7 but it does further comprise a funnel 16' disposed within the container 3' such that the inlet 16A' of the funnel 16' is disposed directly below the spinneret to receive the fiber mesh 8' therein.
  • the outlet 16B' of the funnel 16' extends through the hole 9' .
  • the funnel 16' is used to aid in the creation of the vortex fluid flow 10' such that the vortex fluid flow 10' extents into hole 9' . In this way, the fiber mesh 8' is assisted to be drawn into the vortex fluid flow 10' and thereby twist and form the fiber yarn 14.
  • Fig. 3 is a schematic diagram of the apparatus of Fig. 1 wherein multiple spinnerets (IA, IB, 1C, ID) are used to form a single fiber yarn 14 from respective polymer jets (5A, 5B, 5C, 5D) .
  • multiple spinnerets IA, IB, 1C, ID
  • by varying the number of polymer jets it is possible to vary the diameter of the yarn 14.
  • a filament in the form of a flexible rod 17 is passed through hole 9 at the bottom of container 3 to cause fiber yarn 14 to form around the flexible rod 17.
  • An example of a tubular fiber yarn can be seen from Fig. 4D showing a SEM image at 300Ox magnification .
  • Finer diameter electrospun fiber yarns or single electrospun fibers are drawn individually from different containers and collected into a central container where there is a rapid vortex such that a few electrospun fiber yarns or electrospun fibers are twisted together.
  • a higher feedrate of polymer solution to spinneret 1 or using multiple spinnerets (Fig. 3) during electrospinning may yield higher production of continuous electrospun fiber yarn 14.
  • the use of multiple spinnerets may result in a hollow yarn, as seen in Fig. 4, when a vortex is created in the container 3. As the formed fibers are sucked into the vortex fluid flow 10, a hollow space is created in the middle of the yarn 14 due to the spiral forces of the vortex fluid flow 10. The hollow yarn 14 forms due to evaporation of the non- solvent from the core of the yarn.
  • the flexible rod or filament 17 (refer to Fig. 3) may be used to form the hollow fiber as described above.
  • the diameter of the fiber yarn 14 is able to be varied by:
  • Fig. 8 shows a schematic diagram of an apparatus 100" having a number of technical features that are the same as the apparatus 100 described above, which are indicated by the same reference numeral but with an end quotation symbol (") .
  • the apparatus 100" does not have a ring electrode 7, vortex fluid flow 10, pump 11, opening 12 and liquid conduit 18.
  • the vortex fluid flow 10 does not extend through the hole 9" located in the bottom of container 3"
  • the barbed stick may be used to latch onto the electrospun fiber mesh 8" on the surface of the non- solvent so as to draw the fiber yarn 14" through the hole 9" located at the bottom of the container 3" after which normal drawing process may proceed.
  • the formed fiber yarn 14, after passing through the hole 9, is able to be passed through a series of blowers and/or heating elements (not shown) to dry the fiber yarn before collecting on the roller 15.
  • the fiber yarn is also able to be mechanically twisted and/or braided after it is drawn out from the hole 9 of the container 3 before being wound onto a roller 15.
  • Example 1 Yarn drawn into the vortex using a single spinneret
  • FIG. 1 The apparatus of Fig. 1 was used on this experiment.
  • a hole (9) with a diameter of 5 mm located in the bottom of the container (3) having a diameter of 35cm was filled with water as the non-solvent.
  • the water flowed from the hole (9) under gravity to create the vortex fluid flow (10) of the water.
  • Water was dispelled from the container (3) into the feed tank (13) .
  • the pump (11) recycled the water back to the container (3) via liquid conduit (18) at a pump speed of 900 1/hr.
  • the diameter of liquid conduit (18) is 15 mm.
  • the polymer solution was prepared by dissolving Polyvinylidene fluoride-co-Hexafluoropropylene (PVDF-co- HFP) (M w 455,000) from Aldrich of St. Louis, Missouri, United States of America in a mixture of 40% dimethylacetamide and 60% acetone before being heated to 60 0 C.
  • the concentration of PVDF-co-HFP in solution was 0.12g/ml.
  • Electrospinning was carried using a high voltage power supply (2) from Gamma High Voltage Research Inc of Ormond Beach, Florida, United States of America. A voltage of 12kV was applied to the polymer solution. A kd Scientific syringe pump was used to provide constant feedrates of lml/hr, 2ml/hr, 5ml/hr, 8ml/hr, 12ml/hr to the spinneret (1) . The inner diameter of the spinneret nozzle (IA) was 0.21 mm. The continuous yarn collection timing without breakage was noted up to 1 minute for the different feedrates.
  • IA inner diameter of the spinneret nozzle
  • Fig. 4A is an SEM image at 400Ox magnification of the poly (vinylidene fluoride) electrospun fiber yarn formed using a feedrate of 5ml/hr.
  • Fig. 4B is an SEM image at 300Ox magnification of a cross-sectional view of the fiber yarn of Fig. 4A. It can be seen from Fig. 4A and Fig. 4B that a micro-sized diameter fiber yarn was produced from nano-sized diameter fibers.
  • Example 2 Yarn drawn into the vortex using single spinneret with a funnel below
  • FIG. 2 The apparatus of Fig. 2 was used on this experiment.
  • a funnel (16') with an outlet (16B') having a diameter of 6 mm was located at the bottom of container (3') having a diameter of 24cm such that the outlet (16B') extended from the hole (9')-
  • the container (3') was filled with water as the non-solvent.
  • the funnel (16') aided in the creation of the vortex fluid flow (10') in the container (3') and allowed the fiber yarn (14') to be drawn from the funnel outlet (16B' ) easily.
  • the polymer solution was prepared by dissolving Polycaprolactone (PCL) (M n 80000) from Aldrich of St Louis, Missouri, United States of America in a mixture of 80% dichloromethane and 20% N,N-dimethylformamide.
  • PCL Polycaprolactone
  • the concentration of PCL in solution was 0.14g/ml.
  • Electrospinning was carried out by connecting a high voltage power supply from Gamma High Voltage Research HV Inc of Ormond Beach, Florida, United States of America. A voltage of 1OkV was applied to the polymer solution. A kd Scientific syringe pump was used to provide constant feedrates of lml/hr, 2ml/hr, 5ml/hr, 10ml/hr to the spinneret (I' ) • The inner diameter of the spinneret nozzle (IA' ) was 0.21 mm.
  • Example 3 Yarn drawn into the vortex using multiple spinnerets to fabricate hollow yarn
  • the apparatus (100') of Fig. 2 with five spinnerets was used in this experiment.
  • a funnel (16' ) with an outlet (16B' ) having a diameter of 6 mm was located at the bottom of container (3') having a diameter of 24cm such that the outlet (16B') extended from the hole (9').
  • the container (3') was filled with water as the non-solvent. Water was dispelled from the container (3' ) into the feed tank (13').
  • the pump (H') recycled the water back to the container (3') via liquid conduit (18') at a pump speed of 900 1/hr.
  • the diameter of liquid conduit (18' ) is- 15 mm.
  • the polymer solution was prepared by dissolving Polycaprolactone (PCL) (M n 80000) from Aldrich of St Louis, Missouri, United States of America in a mixture of 75% chloroform and 25% methanol. The concentration of PCL in solution was 8wt%. Electrospinning was carried out by connecting a high voltage power supply from Gamma High Voltage Research HV Inc of Ormond Beach, Florida, United States of America. A voltage of 1OkV was applied to the polymer solution. A kd Scientific syringe pump was used to provide a constant feedrate of 15ml/hr to five spinnerets arranged around the vortex fluid flow (10') on the surface of the water. The inner diameter of -the nozzle (IA') of each of the spinnerets used here is 0.21 mm.
  • Fig. 4C is an SEM image at 200Ox magnification of the poly (caprolactone) electrospun fiber yarn collected at a speed of 63 m/min in this experiment.
  • the diameter of the yarn is 50 ⁇ m
  • Fig. 4D is an SEM image at 300Ox magnification of a cross-sectional view of the fiber yarn of Fig. 4C. It can be seen that a hollow fiber yarn was produced by using multiple spinnerets.
  • Example 4 - Yarn drawn without the use of vortex The apparatus (100") of Fig. 8 was used in this experiment .
  • a hole (9") with a diameter of 1 mm was located in the bottom of the container (3") having a diameter of 24cm filled with water as the non-solvent. Water was dispelled from the container (3") into the feed tank (13") .
  • the polymer solution was prepared by dissolving
  • PCL Polycaprolactone
  • Electrospinning was carried out by connecting a high voltage power supply from Gamma High Voltage Research HV Inc of Ormond Beach, Florida, United States of America. A voltage of 1OkV was applied to the polymer solution. A kd Scientific syringe pump was used to provide a constant feedrate of lml/hr to the spinneret (1") . The inner diameter of the spinneret nozzle (IA") used was 0.21 mm.
  • Fig. 6 is a photograph diagram of a tape-like electrospun fiber yarn drawn at a speed of 1 m/min formed in this experiment.
  • Fig. 7 is an SEM image at 80Ox magnification of a tape-like electrospun fiber yarn drawn at a speed of
  • a thicker yarn is able to be spun in the absence of a vortex.
  • the non-solvent acts as a support for the fiber yarn (14") to prevent or inhibit it from breakage. Additionally, as the fibers are removed from the hole (9"), non-solvent is drawn down into the hole (9") and assists in pushing the fibers together to thereby form the yarn (14") .
  • Fiber yarns produced by an embodiment described herein can be used for a variety of purposes such as, but not limited to, production of composites, filtration media, gas separation, sensors or biomedical engineering. Moreover, such fiber yarns can be used in the healthcare industry as tissue scaffolds whereby the fiber yarns impart desired mechanical strength. Furthermore, fibers with diameters from the nanometer to sub-micron scale that impart desired properties can be electrospun together to form fiber yarns for the textile industry.
  • the formation of a vortex within the non-solvent assists in twisting the electrospun fibers and thereby forms the yarn.
  • the non-solvent provides a support for the fibers as they are electrospun to prevent or inhibit them from breakage.
  • drawing the fibers through the outlet conduit promotes formation of the yarn by drawing the fibers together by the flow regime within the receptacle as non- solvent passes through the outlet conduit.
  • the use of a vortex enables production of an electrospun yarn at relatively high rates
  • the absence of the vortex enables production of an electrospun yarn at lower rates (ie about 1 m/min) , which is particularly useful when additives are to be added to the yarn.
  • the slower production rate results in a longer residence time within the receptacle which allows a greater time for adsorption when an additive to be adsorbed is present in the non-solvent.
  • additives may be added onto the fiber mesh formed in the non-solvent.
  • the advantage of adding additives onto the mesh is that the additives are encapsulated unto the yarn as it is formed.
  • the non-solvent may be mechanically agitated or the container may be rotated to cause non- solvent to rotate within the container and thereby promote formation of the vortex fluid flow.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

La présente invention concerne un procédé de production d’un fil constitué de fibres supposant une étape d’électrofilage d’une fibre au sein d’un non-solvant contenu dans un récipient, ledit récipient comprend un conduit de sortie permettant au non-solvant de s’écouler, les dimensions du conduit de sortie sont prévues pour que tandis que le non-solvant s’en écoule le fil se forme au sein de celui-ci à partir des fibres électrofilées.
PCT/SG2006/000208 2005-07-25 2006-07-25 Procédé et appareil de production de fil constitué de fibres WO2007013858A1 (fr)

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Cited By (12)

* Cited by examiner, † Cited by third party
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WO2009127170A3 (fr) * 2008-04-15 2009-12-03 Elmarco S.R.O. Procédé de production de nanofibres à partir de copolymères et de terpolymères fluorés par filage électrostatique, nanofibres et tissus
CN101845675A (zh) * 2010-05-10 2010-09-29 北京化工大学 制备沿纤维轴单向排列纳米长纤维的静电纺丝方法及装置
CN102321927A (zh) * 2011-08-31 2012-01-18 青岛大学 一种旋转圆盘感应起电式静电纺丝装置
US8582935B2 (en) 2011-02-11 2013-11-12 AMI Research & Development, LLC Correction wedge for leaky solar array
CN104726943A (zh) * 2015-03-06 2015-06-24 北京化工大学 一种龙卷旋风式制备纳米捻线静电纺丝喷头装置
CN104775170A (zh) * 2015-04-30 2015-07-15 广西师范学院 一种静电纺丝的连续收集装置
CN105862210A (zh) * 2016-04-29 2016-08-17 河南工程学院 抗菌纳米纤维纱线及其制备方法
CN107523887A (zh) * 2017-10-20 2017-12-29 上海工程技术大学 环形静电喷丝机构以及静电喷丝装置
CN108774758A (zh) * 2018-05-28 2018-11-09 泽塔纳米科技（苏州）有限公司 一种纳米纤维的制备方法
WO2023057403A1 (fr) * 2021-10-06 2023-04-13 Cytec Industries Inc. Boîtier de filière destiné à être utilisé dans la fabrication de fibres polymères et procédé d'utilisation associé
WO2023057174A1 (fr) * 2021-10-06 2023-04-13 Cytec Industries Inc. Appareil pour une injection de coagulation améliorée pendant la fabrication de fibres polymères et procédé d'utilisation associé
CN118441417A (zh) * 2024-07-05 2024-08-06 烟台沃德麦克斯纳米科技有限公司 一种静电纺丝纤维膜的生产设备

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RU2093618C1 (ru) * 1995-03-16 1997-10-20 Товарищество с ограниченной ответственностью "Везувий-11" Способ получения волокна из термопластичного материала
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US20030190383A1 (en) * 2001-07-04 2003-10-09 Hag-Yong Kim Electronic spinning apparatus, and a process of preparing nonwoven fabric using the thereof
WO2003057952A1 (fr) * 2002-01-08 2003-07-17 Zimmer Aktiengesellschaft Dispositif et procede de filage avec soufflerie de refroidissement
WO2005064047A1 (fr) * 2003-12-23 2005-07-14 Virginia Commonwealth University Procede de fabrication de fibres par electrofilage a des pression elevees
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Publication number Priority date Publication date Assignee Title
WO2009127170A3 (fr) * 2008-04-15 2009-12-03 Elmarco S.R.O. Procédé de production de nanofibres à partir de copolymères et de terpolymères fluorés par filage électrostatique, nanofibres et tissus
CN101845675A (zh) * 2010-05-10 2010-09-29 北京化工大学 制备沿纤维轴单向排列纳米长纤维的静电纺丝方法及装置
US8582935B2 (en) 2011-02-11 2013-11-12 AMI Research & Development, LLC Correction wedge for leaky solar array
US8824843B2 (en) 2011-02-11 2014-09-02 AMI Research & Development, LLC Leaky mode solar receiver using continuous wedge lens
US8855453B2 (en) 2011-02-11 2014-10-07 AMI Research & Development, LLC Quadratic phase weighed solar receiver
CN102321927A (zh) * 2011-08-31 2012-01-18 青岛大学 一种旋转圆盘感应起电式静电纺丝装置
CN104726943A (zh) * 2015-03-06 2015-06-24 北京化工大学 一种龙卷旋风式制备纳米捻线静电纺丝喷头装置
CN104775170A (zh) * 2015-04-30 2015-07-15 广西师范学院 一种静电纺丝的连续收集装置
CN105862210A (zh) * 2016-04-29 2016-08-17 河南工程学院 抗菌纳米纤维纱线及其制备方法
CN107523887A (zh) * 2017-10-20 2017-12-29 上海工程技术大学 环形静电喷丝机构以及静电喷丝装置
CN107523887B (zh) * 2017-10-20 2019-04-05 上海工程技术大学 环形静电喷丝机构以及静电喷丝装置
CN108774758A (zh) * 2018-05-28 2018-11-09 泽塔纳米科技（苏州）有限公司 一种纳米纤维的制备方法
CN108774758B (zh) * 2018-05-28 2021-01-26 泽塔纳米科技（苏州）有限公司 一种纳米纤维的制备方法
WO2023057403A1 (fr) * 2021-10-06 2023-04-13 Cytec Industries Inc. Boîtier de filière destiné à être utilisé dans la fabrication de fibres polymères et procédé d'utilisation associé
WO2023057174A1 (fr) * 2021-10-06 2023-04-13 Cytec Industries Inc. Appareil pour une injection de coagulation améliorée pendant la fabrication de fibres polymères et procédé d'utilisation associé
CN118441417A (zh) * 2024-07-05 2024-08-06 烟台沃德麦克斯纳米科技有限公司 一种静电纺丝纤维膜的生产设备

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