WO2013096095A1 - Fibres électrofilées par fusion contenant des micro- et des nano-couches et procédé de fabrication - Google Patents

Fibres électrofilées par fusion contenant des micro- et des nano-couches et procédé de fabrication Download PDF

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Publication number
WO2013096095A1
WO2013096095A1 PCT/US2012/069629 US2012069629W WO2013096095A1 WO 2013096095 A1 WO2013096095 A1 WO 2013096095A1 US 2012069629 W US2012069629 W US 2012069629W WO 2013096095 A1 WO2013096095 A1 WO 2013096095A1
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Prior art keywords
fiber
layers
fibers
electroprocessing
polymers
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PCT/US2012/069629
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English (en)
Inventor
Eugene G. Joseph
Naresh BUDHAVARAM
Roop MAHAJAN
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Virginia Tech Intellectual Properties, Inc.
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Priority to US14/366,323 priority Critical patent/US20140357144A1/en
Publication of WO2013096095A1 publication Critical patent/WO2013096095A1/fr
Priority to US15/068,945 priority patent/US20160194796A1/en

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Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • D—TEXTILES; PAPER
    • 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
    • D01D5/0023—Electro-spinning characterised by the initial state of the material the material being a polymer melt
    • 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
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • 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
    • D01D5/42—Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments
    • D01D5/423—Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments by fibrillation of films or filaments
    • 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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • 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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D01F6/06—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene
    • 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
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43825—Composite fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43838—Ultrafine fibres, e.g. microfibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/559—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving the fibres being within layered webs
    • 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
    • Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2008—Fabric composed of a fiber or strand which is of specific structural definition
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/637—Including strand or fiber material which is a monofilament composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material

Definitions

  • This invention pertains to electrospinning for the production of nanofibers and nano fiber webs, and, more particularly, the invention is focused on producing nanofibers and nano fiber webs from a polymer melt.
  • Electrospinning is a process that is used to produce nanofibers and nanofiber webs.
  • the nanofibers and nanofiber webs have been evaluated for use in a wide range of applications including without limitation in filtration, protective doming, drug delivery, tissue engineering, and nanocomposites.
  • Solution electrospinning can pose a significant safety problem during manufacture since most solvents used for synthetic polymers are highly flammable, as well as toxic or carcinogenic.
  • the solvents employed in solution based electrospinning also pose additional concerns such as solvent cost, solvent recovery, low production rates, and limiting limited biomedical applications due to residual toxic solvent.
  • solvent-free processes such as melt processes for the manufacture of nanofibers.
  • co-extrusion technology is combined with electroprocessing technology to produce nanofibers containing multiple layers of materials.
  • multilayered nanofibers produced by electroprocessing are effectively "delaminated” (i.e., the layers within the fibers are separated) by sonication or other suitable energy application techniques.
  • a "solvent-free” process is used to create fibrous materials that have significantly higher surface areas than currently manufactured nanofibers.
  • the process combines co-extrusion where two polymer resins in the molten state are arranged to give alternating layers via feed blocks or layer multipliers, with melt electrospinning (or other suitable electroprocessing).
  • melt electrospinning or other suitable electroprocessing.
  • nonwoven webs that have hundreds to over a thousand layers within each microfiber can be created. These webs can be subsequently exposed to ultrasonication to create delamination of the layers which result in nanolayer melt electrospun (NME) fibrous webs.
  • NME nanolayer melt electrospun
  • the multilayer electrospun fibers have been evaluated using electron microscopy both before and after sonication. Experiments have demonstrated that melt electrospun fibers produced according to the invention with 257 alternating layers can be successfully produced and delaminated by ultrasonication.
  • the invention includes melt electrospun fibers and matrices, such as non-woven webs, of fibers that contain alternating layers, and their method of production.
  • the invention includes nanolayer thick fibers (e.g., fiber ribbons) created by delamination of melt electrospun fibers having alternating layers of polymers.
  • the invention includes matrices of these nanolayer thick fibers, in laminated or delaminated form.
  • the inventive matrices can have substances of interest deposited on them (e.g., bioactive agents, catalytic agents, fire retardant chemicals, etc.).
  • two extruders deliver different polymers to a 3 layer feedblock where layering of the melt occurs and this 3 layer melt stream is fed to a single orifice die.
  • a high voltage is applied to a flat plate collector placed at a suitable distance from the die and electrospun fibers are formed and collected on the flat plate.
  • the 3 layer melt stream is fed to a layer multiplying unit where the melt layers are multiplied (multiplying depends on the number of multipliers used).
  • a melt stream with 257 layers, when 7 multipliers are used, is fed to the single orifice die.
  • a high voltage is applied to a flat plate collector placed at a suitable distance and electrospun fibers are collected on the flat plate.
  • melt electrospun webs that have about 257 alternating layer fibers are exposed to ultrasonication (or other energy application or chemical application) to create nanolayer thick fibers due to delamination of the layers. Delamination can be achieved by other mechanisms such as exposure to chemicals such as chloroform,
  • Figure 1(a) is a schematic of the layer multiplying process that occurs when using two layers as input to the layer multiplying process.
  • Figure 1 (b) is a schematic of the cross-section of a fiber with multiple layers of two different polymers.
  • Figures 2A-C are, respectively, schematic drawings of a system for producing multilayer electrospun fibers according to the invention with a flat plate collector (Figure 2A), a rotary drum collector ( Figure 2B), and a wide width die in combination with a rotary drum collector ( Figure 2C).
  • Figure 3 illustrates a simplified process for delaminating fibers in a fibrous mat formed by melt electroprocessing multiple polymers according to the invention.
  • Figure 4 is a scanning electron micrograph (SEM) of a melt electrospun fiber described in Example 1 that has 257 alternating layers of polycaopactone (PCL) and polyethylene (PE).
  • SEM scanning electron micrograph
  • Figure 5 is a SEM image of a melt electrospun fiber described in Example 2 that has 257 alternating layers of PCL and PE.
  • Figure 6 is a SEM image of a melt electrospun fiber web described in Example 7 that has 257 alternating layers of PCL and PE after ultarsonication which shows delamination of the layers after sonication.
  • Figure 7 is an SEM image of a melt electrospun fiber web described in Example 8 where PCL and PP layers in the fibers are delaminated by exposure to chloroform with slight agitation.
  • Figure 8 is an SEM image of a melt electrospun fiber web described in Example 9 where PCL and PE layers in the fibers are delaminated by exposure to chloroform with slight agitation.
  • Co-extrusion in the context of the present invention is a process by which two polymer resins in the molten state are arranged via feed blocks or layer multipliers to give alternating layers.
  • the number of layers in the final extruded form e.g., film or microfiber
  • feedblock technology is typically used to produce films with approximately 3 to 7 layers
  • layer-multiplying technology is used to produce hundreds to thousands of layers within 25-50 micron thick films.
  • the layer multiplying process is shown schematically in Figures la and lb.
  • a two component (AB) co-extrusion system which could include, for example, two single screw extruders each connected by a melt pump to a co-extrusion feedblock.
  • the feedblock combines polymeric material (a) and polymeric material (b) in an (AB) layer configuration (see leftmost portion of Figure la).
  • Melt pumps (not shown) control the two melt streams that are combined in the feedblock as two parallel layers.
  • the relative layer thickness that is, the ratio of A to B can be varied (as shown, the ratio of the top layer to the bottom layer). From the feedblock, the melt goes through a series of multiplying elements.
  • a multiplying element first slices the AB structure vertically, and subsequently spreads the melt horizontally. The flowing streams recombine, doubling the number of layers.
  • An assembly of n multiplier elements produces an extrudate with the layer sequence (AB) X where x is equal to (2) n and n is the number of multiplying elements to form a multilayer stack (as depicted in the right most portion of Figure la).
  • Figure lb is a cross-sectional view of a fiber with multiple layers produced by co-extrusion (it being recognized that the layers in a co-extruded fiber may not be flat as depicted in Figure lb; rather, the individual layers may be curved or have other configurations, but will form distinct regions in the fiber).
  • PCL polycaprolactone
  • polyolefms e.g., polyolefms
  • thermally stable and melt processable natural polymers e.g., those occurring naturally in a plant or animal
  • plasticized cellulose acetate e.g., plasticized cellulose acetate
  • electroprocessing or “electrodeposition” broadly include all methods of electrospinning, electrospraying, electroaerosoling, and electro sputtering of materials, including combinations of two or more of such methods, as well as any other method wherein materials are streamed, sprayed, sputtered, or dripped across an electric field toward a target.
  • a material can be electroprocessed from one or more grounded reservoirs in the direction of a charged substrate or from charged reservoirs toward a grounded target.
  • Electroprocessing can be performed using one or a plurality of nozzles, and, in the case of using multiple nozzles, each nozzle can be connected to a single reservoir or each can be connected to a different reservoir where each reservoir contains the same or a different melt.
  • the size of the nozzles can be varied to provide for increased or decreased flow out of the nozzles, and a pump or a plurality of pumps can be used to control flow from the reservoir(s).
  • ElectiOspinning is generally defined as a process by winch fibers are formed from melt by streaming the melt through an orifice. In an embodiment of this invention, elecrospinning is achieved by applying a voltage to a collector and the melt is streamed from through the orifice to the collector. Other configurations are possible.
  • Electroaerosoling is generally defined as a process by which droplets are formed from a melt by streaming an electrically charged solution or melt through an orifice,
  • Electroprocessing techniques are well known in the art. See, for example, U.S. Patent 7,759,082, U.S. Patent 7,615,373, U.S. Patent 7,374,774, U.S. Patent 6,787,357, U.S. Patent 8,282,712, U.S. Patent 6,592,623, U.S. Patent 8,282,712, U.S. Patent 8,277,712, U.S. Patent 8,277,711, U.S. Patent 8,277,706, U.S. Patent 8,262,958, U.S. Patent 8,257,628, U.S. Patent 8,247,335, U.S. Patent 8,246,730, U.S. Patent 8,241,729, U.S. Patent 8,178,199, U.S.
  • Patent 7,291,300 U.S. Patent 7,134,857, U.S. Patent 7,070,640, and U.S. Patent 6,838,005, each of which are herein incorporated by reference.
  • natural fibers e.g., collagen, fibrin, etc.
  • synthetic fibers and combinations thereof can be produced from solutions by electroprocessing.
  • the invention contemplates a co-extruded stream of two or more polymer melts (e.g., polymer blend streams), which can be multiplied or not multiplied, being subject to electroprocessing to produce fibers with a plurality of layers therein.
  • the fibers will have at least two layers (Examples below show co-extruded, electroprocessed fibers with three layers, and show the order of the layers does not impact the ability to form fibers), and possibly 50 to 100 or more layers (Examples below show co-extruded, electroprocessed fibers with 247 layers).
  • the fibers produced by co-extrusion and electroprocessing according to the invention are multilayered and have a diameter of ⁇ or less.
  • fibers of 50 ⁇ or less have been produced, and some multilayer fibers having diameters as small as 5-10 ⁇ have been produced. Furthermore, on delamination of the multilayer fibers, ribbon shaped fibers which have thicknesses on the order of nanometers have been produced.
  • the electroprocessed materials form a "matrix".
  • Matrices are comprised of multilayer fibers, or blends of multilayer fibers and droplets of any size or shape.
  • Matrices can be single structures or groups of structures, and can be formed through one or more electroprocessing methods using a plurality of materials. Matrices can be engineered to possess specific porosities.
  • Substances of interest can be deposited within, anchored to, or placed on matrices.
  • Exemplary substances of interest can include bioactive agents (e.g., proteins, nucleic acids, antibodies, anesthetics, hypnotics, sedatives, sleep inducers, antipsychotics, antidepressants, antiallergics, antianginals, antiarthritics, antiasthmatics, antidiabetics, antidiarrheal drugs, anticonvulsants, antigout drugs, antihistamines, antipruritics, emetics, antiemetics, antispasmodics, appetite suppressants, neuroactive substances,
  • bioactive agents e.g., proteins, nucleic acids, antibodies, anesthetics, hypnotics, sedatives, sleep inducers, antipsychotics, antidepressants, antiallergics, antianginals, antiarthritics, antiasthmatics, antidiabetics, antidiarr
  • immunosuppressants hormone agonists, hormone antagonists, vitamins, antimicrobial agents, antineoplastics, antacids, digestants, laxatives, cathartics, antiseptics, diuretics, disinfectants, fungicides, ectoparasiticides, antiparasitics, heavy metals, heavy metal antagonists, chelating agents, alkaloids, salts, ions, autacoids, digitalis, cardiac glycosides, antiarrhythmics, antihypertensives, vasodilators, vasoconstrictors, antimuscarinics, ganglionic stimulating agents, ganglionic blocking agents, neuromuscular blocking agents, adrenergic nerve inhibitors, anti-oxidants, anti-inflammatories, wound care products, antithrombo genie agents, antitumoral agents, antithrombogenic agents, antiangiogenic agents, antigenic agents, wound healing agents, plant extracts, growth factors, growth hormones, cytokines, immunoglobulins, osteoblasts
  • Figures 2A-C shows schematic drawings of an exemplary electroprocessing configuration where a voltage controller 10 is used to charge a target 12 or 12'.
  • the target 12 is a flat panel.
  • the target 12' is a mandrel or rotary drum.
  • the target 12 may be rotated during
  • the Target 12 or 12' can be of many different shapes and sizes to suit the needs of the application.
  • FIGS. 2A-2C show a source 13 having a feedblock 14 and multiplier section 15 that allow combining a plurality of polymers from polymer sources 16a-16n.
  • the multiplier section 15 can have zero to a plurality of multipliers (e.g., 2, 3, 7, 10, 20, etc.) depending on the application. With zero multipliers, the feedblock 14 will be used to introduce a layered polymer melt for electroprocessing. However, in some
  • the fibers produced will have at least two different layers of two different polymers (the Examples below show some fibers produced with three different layers having two different polymers, wherein in one Example the outer layers are PE and the inner layer is PCL and in another Example the inner layer is PE and the outer layer is PCL). While the Examples below show combining two polymers into one multilayered fiber, it will be recognized that a plurality of the polymers can be combined by co-extrusion. Thus, fibers having layers of three different polymers, four different polymers, five different polymers, etc. can be made according to the present invention.
  • Figures 2A-C are depicted with polymer sources 16A-16N, where N equals the number of polymers being combined. Further, the polymers in the polymer sources 16A-16N may themselves be polymer blends.
  • Figures 2A-2C show a single source 13.
  • the polymers provided by each of the sources can be the same or different.
  • different operational designs can be used for each of the sources to achieve the formation of multilayer fibers of different diameter as well as mixtures of multilayer fibers and multilayer droplets.
  • the polymers provided by source 13 have at least two different layers of two different polymers.
  • the thickness of each of the layers of polymers in the fiber can be varied by a variety of means including by control of pumps (not shown) from the polymer sources 16A-16N.
  • the stream of polymer 18 emanating from the nozzles or "tips" 20 or 20' directed towards the target 12 or 12' can be controlled.
  • source 13 could supply a stream 18 of multilayer fibers or a mixture of multilayer fibers and droplets towards target 12, or source 13 could supply a stream 22 of multilayer fiber which may include branching.
  • Control of the streams can be achieved by a variety of mechanisms including controlling polymer supply pumps, regulating the nozzle 20 or 20' sizes in the sources 13, regulating the charge on the polymer and/or target 12 or 12', etc.
  • the target 12 or 12' will receive a mass of multilayer fibers generally configured as a non-woven mat.
  • the multilayer fibers can have some crosslinking with the polymers in adjacent fibers, and can contain multilayer droplets interspersed with the multilayer fibers.
  • the bottom of Figure 2C shows a plan view of the tip 20' where there are multiple orifices for emitting multiple streams of polymer during electroprocessing. With this design a thick mat can be created over a wide area in a short term.
  • Figure 3 illustrates the process of converting the multilayer fibers created by coextrusion/electroprocessing to ribbon shaped fibers, as shown by Example 7 below.
  • the fibrous mat 50 from the electrospinning target is placed in a delaminating device 52 such as a sonicating bath.
  • the sonicating bath 50 can contain any suitable fluid (e.g., water, solvents, etc.) for permitting ultrasonic energy to interact with the fibers such as, for example, a mixture of isopropanol and water.
  • delamination may be achieved chemically by, for example, exposure to chloroform, ethyl acetate, or other solvent.
  • chemical and physical techniques may be used in combination, for example, by exposure to chloroform or ethyl acetate which promotes delamination (e.g., by a rinse) in combination with exposure to energy (e.g., sonication). Delamination can be achieved fairly quickly. For example, sonication of a multilayered chloroform or ethyl acetate which promotes delamination (e.g., by a rinse) in combination with exposure to energy (e.g., sonication). Delamination can be achieved fairly quickly. For example, sonication of a multilayered
  • polyethylene/polycaprolactone fiber of less than 100 ⁇ in diameter achieved
  • Figure 3 shows the delaminated fibers 54 can be retrieved as a mat from the delaminator (sonicating bath) 52.
  • the delaminated fibers 54 are comprised of a plurality of ribbon shaped fibers, typically on the order of nanometers in thickness where each individual ribbon is of one distinct material.
  • Figure 3 also shows that active agents 56 (such as biological active agents, catalytic agents, etc.) can be deposited on the delaminated fibers 54. This can be accomplished by spraying the active agent onto the mat, dipping the mat into a pool of active agents, electroplating the active agent onto the mat, and by many other means recognized by those of skill in the art.
  • Figure 3 shows application of the active agent 56 to the delaminated fibers 54, in some applications, active agents could simply be applied to the mat of multilayer fibers 50.
  • the fibrous mats produced according to the invention can be used in a wide variety of applications including without limitation filtration, protective clothing, drug delivery, tissue engineering, and nano composites.
  • the fibrous materials have
  • the fibrous materials are manufactured in a "solvent free” manner which avoids many of the manufacturing risks and costs encountered in current electrospinning processes.
  • the polymeric components are melted in a single screw extruder and transported via gear pumps to a 3 layer feedblock, where the two polymers are formed into a single flow stream of 3 alternating layers.
  • This 3 layer melt stream is delivered to a layer multiplier that has seven multipliers where the 3 layer stream is cut and stacked seven times to have final melt stream that has 257 alternating layers.
  • This melt stream is delivered to a single orifice die and electrospun into fibers by the application of a high voltage to a flat plate collector which is positioned at a suitable distance across from the die.
  • the size and structure of the electrospun fibers were obtained using a LEO (Zeiss) 1550 field emission scanning electron microscope (FE-SEM) in the secondary electron mode. Scanning electron microscopy images were obtained at different magnifications and the fiber diameters were measured using image analysis software.
  • melt electrospun fibers and webs were immersed in a water / isopropanol (w/w 80/20) mix and exposed to sonication using a Tekmar Sonic Disruptor at different intensities and time periods. These materials were viewed in the SEM to determine if delamination of the layers occurred and to what extent it occurred.
  • a melt electrospun fiber and web of the present invention was made using polycaprolactone (PCL) resin (CAPA 6250 available from Persorp UK Ltd) and polyethylene (PE) resin (Epolene C-10 available from Westlake Chemical Corporation).
  • PCL polycaprolactone
  • PE polyethylene
  • the polymer pellets were fed to two extruders connected to gear pumps to control the flow, which fed the melt streams to a 3 layer feedblock. Both extruders and the feedblock were maintained at about 356 °F.
  • the feedblock split the two melt streams and arranged them in an alternating fashion into a 3 layer melt stream on exiting the feedblock, with the outer layers being PCL.
  • the PCL : PE ratio was maintained at a 50:50 ratio by adjusting the gear pumps and the flow rate of both gear pumps were maintained at 1 revolution per minute (RPM).
  • the layered melt stream was fed to a layer multiplier that had 7 multipliers, which cut and stacked the layered stream 7X and resulted in a melt stream that had 257 layers upon exiting the layer multiplier.
  • the layer multiplier was maintained at about 356 °F.
  • This stream with 257 alternating layers was fed to a single orifice die which was maintained at about 356 °F, and a voltage of 58 kV was applied to a flat plate collector placed 6 inches away from the die to electrospin a fibrous web.
  • the resulting web had each fiber comprised of 258 alternating PCL / PE layers.
  • a scanning electron micrograph (SEM) of the electrospun fiber produced according to this Example 1 is presented in Figure 4. The diameter of the fiber is approximately 5-10 ⁇ .
  • a melt electrospun fiber and web, comprising 257 layer fibers was prepared according to the procedure described in Example 1, except the voltage applied was 42 kV.
  • a melt electrospun fiber and web, comprising 257 layer fibers was prepared according to the procedure described in Example 1 , except the flow rate of both gear pumps were maintained at 2 RPM's, the voltage was 60 kV and the flat plate collector was placed 4 inches away from the die.
  • a melt electrospun fiber and web of the present invention was made using
  • PCL polycaprolactone
  • PE polyethylene
  • Epolene C-10 available from Westlake Chemical Corporation
  • the polymer pellets were fed to two extruders connected to gear pumps to control the flow, which fed the melt streams to a 3 layer feedblock. Both extruders and the feedblock were maintained at about 320 °F.
  • the feedblock split the two melt streams and arranged them in an alternating fashion into a 3 layer melt stream on exiting the feedblock, with the outer layers being PCL.
  • the PCL : PE ratio was maintained at a 50:50 ratio by adjusting the gear pumps and the flow rate of both gear pumps were maintained at 0.5 RPM's.
  • a melt electrospun fiber and web of the present invention was made using polyethylene (Epolene C-10 available from Westlake Chemical Corporation) and polypropylene (PP) resin (PP 3746G available from Exxon-Mobile Corporation).
  • the polymer pellets and granules were fed to two extruders connected to gear pumps to control the flow, which fed the melt streams to a 3 layer feedblock. Both extruders and the feedblock were maintained at about 392 °F.
  • the feedblock split the two melt streams and arranged them in an alternating fashion into a 3 layer melt stream on exiting the feedblock, with the outer layers being PE.
  • the PE : PP ratio was maintained at a 50:50 ratio by adjusting the gear pumps and the flow rate of both gear pumps were maintained at 0.5 RPM.
  • This stream with 3 alternating layers was fed to a single orifice die which was maintained at about 392 °F, and a voltage of 60 kV was applied to a flat plate collector placed 3 inches away from the die to electrospin a fibrous web.
  • the resulting web had each fiber comprised of 3 alternating PE / PP layers.
  • a melt electrospun fiber and web, comprising 3 layer fibers was prepared according to the procedure described in Example 5, except that PCL was substituted for PE, the PCL extruder temperature was maintained at 356 °F, the PP extruder and feedblock
  • the die temperature was maintained at 536 °F
  • the voltage was 62 kV
  • the flat plate collector was placed 10 inches away from the die.
  • a melt electrospun fiber web described in Example 1 was immersed in a
  • a melt electrospun fiber and web of the present invention was made using
  • PCL polycaprolactone
  • PP polypropylene
  • the polymer pellets and granules were fed to two extruders connected to gear pumps to control the flow, which fed the melt streams to a 3 layer feedblock. Both extruders and the feedblock were maintained at about 356 °F.
  • the feedblock split the two melt streams and arranged them in an alternating fashion into a 3 layer melt stream on exiting the feedblock, with the outer layers being PCL.
  • the PCL : PP ratio was maintained at a 50:50 ratio by adjusting the gear pumps and the flow rate of both gear pumps were maintained at 1 revolution per minute (RPM).
  • the layered melt stream was fed to a layer multiplier that had 7 multipliers, which cut and stacked the layered stream 7X and resulted in a melt stream that had 257 layers upon exiting the layer multiplier.
  • the layer multiplier was maintained at about 356 °F.
  • This stream with 257 alternating layers was fed to a single orifice die which was maintained at about 356 °F, and a voltage of 63 kV was applied to a flat plate collector placed 10 inches away from the die to electrospin a fibrous web.
  • the resulting web had each fiber comprised of 257 alternating PCL / PP layers.
  • FIG. 7 shows an SEM of the fibrous material where at least a portion of the layers of the multilayer melt electrospun fibers have been delaiminated.
  • a melt electrospun fiber and web of the present invention was made using
  • PCL polycaprolactone
  • PE polyethylene
  • RPM revolution per minute
  • the layered melt stream was fed to a layer multiplier that had 7 multipliers, which cut and stacked the layered stream 7X and resulted in a melt stream that had 257 layers upon exiting the layer multiplier.
  • the layer multiplier was maintained at about 356 °F.
  • This stream with 257 alternating layers was fed to a single orifice die which was maintained at about 356 °F, and a voltage of 65 kV was applied to a flat plate collector placed 10 inches away from the die to electrospin a fibrous web.
  • the resulting web had each fiber comprised of 257 alternating PCL / PE layers.
  • FIG. 8 shows an SEM of the fibrous material with delamination of at least a portion of the layers.

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

Abstract

L'invention porte sur des fibres, qui ont deux ou plus de deux couches polymères alternées, et qui sont formées par coextrusion, celle-ci étant suivie par un traitement électrique. Les fibres peuvent être utilisées comme mat non tissé ou comme autre substrat pour une variété d'applications. Un délaminage des fibres à l'aide d'une ultrasonication produit des micro- et nano-couches séparées, des rubans de fibre qui peuvent également être utilisés comme mat non tissé ou comme autre substrat.
PCT/US2012/069629 2011-12-19 2012-12-14 Fibres électrofilées par fusion contenant des micro- et des nano-couches et procédé de fabrication WO2013096095A1 (fr)

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US15/068,945 US20160194796A1 (en) 2011-12-19 2016-03-14 Melt Electrospun Fibers Containing Micro and Nanolayers and Method of Manufacturing

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EP2659034B1 (fr) 2010-12-29 2019-02-20 University of Pittsburgh - Of the Commonwealth System of Higher Education Système et procédé destiné à l'électrofilage sans mandrin
US20140207248A1 (en) * 2013-01-18 2014-07-24 The Trustees Of The Stevens Institute Of Technology Hierarchical multiscale fibrous scaffold via 3-d electrostatic deposition prototyping and conventional electrospinning
WO2020174438A1 (fr) * 2019-02-28 2020-09-03 3M Innovative Properties Company Filaments micro/nano-stratifiés
US20220136140A1 (en) * 2019-02-28 2022-05-05 3M Innovative Properties Company Novel nano-ribbons from multilayer coextruded film

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003080905A1 (fr) * 2002-03-26 2003-10-02 Nano Technics Co., Ltd. Dispositif de fabrication et procede de preparation de nanofibres par un processus de filage par « electro-soufflage »
US20080213417A1 (en) * 2004-12-27 2008-09-04 Michael Allen Bryner Electroblowing web formation
WO2010087812A1 (fr) * 2009-01-27 2010-08-05 Milliken & Company Fibre multicouche, couche fibreuse la comprenant et structure fibreuse consolidée la comprenant
JP2010189792A (ja) * 2009-02-17 2010-09-02 Kato Tech Kk 溶融型紡糸装置、溶融型紡糸方法、熱可塑性樹脂吐出体
JP2011184809A (ja) * 2010-03-04 2011-09-22 Daiwabo Holdings Co Ltd 繊維集合物及びその製造方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3971373A (en) * 1974-01-21 1976-07-27 Minnesota Mining And Manufacturing Company Particle-loaded microfiber sheet product and respirators made therefrom
US5232770A (en) * 1991-09-30 1993-08-03 Minnesota Mining And Manufacturing Company High temperature stable nonwoven webs based on multi-layer blown microfibers
US20050260390A1 (en) * 2004-01-19 2005-11-24 Croft Steven A Coated substrate
US20100047573A1 (en) * 2007-04-11 2010-02-25 Kb Seiren, Ltd. Splittable conjugate fiber
EP2221402A4 (fr) * 2007-11-30 2011-01-12 Daiwabo Holdings Co Ltd Fibre composite ultrafine, fibre ultrafine, son procédé de fabrication et structure de fibre
US8894907B2 (en) * 2008-09-29 2014-11-25 The Clorox Company Process of making a cleaning implement comprising functionally active fibers

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003080905A1 (fr) * 2002-03-26 2003-10-02 Nano Technics Co., Ltd. Dispositif de fabrication et procede de preparation de nanofibres par un processus de filage par « electro-soufflage »
US20080213417A1 (en) * 2004-12-27 2008-09-04 Michael Allen Bryner Electroblowing web formation
WO2010087812A1 (fr) * 2009-01-27 2010-08-05 Milliken & Company Fibre multicouche, couche fibreuse la comprenant et structure fibreuse consolidée la comprenant
JP2010189792A (ja) * 2009-02-17 2010-09-02 Kato Tech Kk 溶融型紡糸装置、溶融型紡糸方法、熱可塑性樹脂吐出体
JP2011184809A (ja) * 2010-03-04 2011-09-22 Daiwabo Holdings Co Ltd 繊維集合物及びその製造方法

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