WO2014160045A1 - Appareils et procédés d'électrofilature - Google Patents

Appareils et procédés d'électrofilature Download PDF

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Publication number
WO2014160045A1
WO2014160045A1 PCT/US2014/025699 US2014025699W WO2014160045A1 WO 2014160045 A1 WO2014160045 A1 WO 2014160045A1 US 2014025699 W US2014025699 W US 2014025699W WO 2014160045 A1 WO2014160045 A1 WO 2014160045A1
Authority
WO
WIPO (PCT)
Prior art keywords
conduit
needle
nozzle
diameter
manifold
Prior art date
Application number
PCT/US2014/025699
Other languages
English (en)
Inventor
Yong Lak Joo
Kyoung Woo Kim
Original Assignee
Cornell University
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 Cornell University filed Critical Cornell University
Priority to US14/458,023 priority Critical patent/US20140353882A1/en
Publication of WO2014160045A1 publication Critical patent/WO2014160045A1/fr
Priority to US15/271,682 priority patent/US20170009380A1/en
Priority to US16/426,626 priority patent/US20190345637A1/en
Priority to US17/549,130 priority patent/US20220098759A1/en

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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
    • D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—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
    • D01D5/34—Core-skin structure; Spinnerette packs therefor

Definitions

  • a technique used to prepare fine polymer fibers is the method of electro-spinning.
  • a conducting fluid e.g., a charged semi-dilute polymer solution or a charged polymer melt
  • a suspended conical droplet is formed, whereby the surface tension of the droplet is in equilibrium with the electric field.
  • Electro-spinning occurs when the electrostatic field is strong enough to overcome the surface tension of the liquid.
  • the liquid droplet then becomes unstable and a tiny jet is ejected from the surface of the spinneret tip. As it reaches a grounded target, the jet stream can be collected as an interconnected web of fine sub-micron size fibers.
  • the resultant films from these non- woven nanoscale fibers have very large surface area to volume ratios.
  • a nozzle or a multi-nozzle system (comprising a plurality of nozzles) for producing nanofibers.
  • the nozzle or multi-nozzle system allows for high throughput nanofiber processing.
  • the nozzle or multi-nozzle system also provides for the preparation of high performance nanofibers - e.g., nanofibers having uniform structures and components.
  • such nanofibers allow for the production of nanofibers that have narrow, uniform diameters.
  • the standard deviation of nanofibers provided, or prepared according to systems and processes described, herein is less than 50% of the average diameter.
  • nozzles for producing nanofibers are suitable or configured for use in an electrospinning apparatus.
  • a nozzle provided herein comprises a first conduit and a second conduit, the first conduit positioned inside the second conduit (e.g., as illustrated in the figures).
  • a nozzle e.g., electrospinning nozzle
  • a nozzle comprises:
  • first conduit the first conduit being enclosed along the length of the conduit by a first wall having an interior and an exterior surface (e.g., the interior surface facing the first conduit and at least a portion of the exterior surface facing the second conduit), and the first conduit having a first inlet (or supply) end and a first outlet end; and b. a second conduit, the second conduit being enclosed along the length of the conduit by a second wall having an interior surface, and the second conduit having a second inlet (or supply) end and a second outlet end.
  • the first conduit is positioned inside the second conduit for a conduit overlap length (e.g., as illustrated by l 1 in the figures).
  • the conduit overlap length is any suitable length, such as about 5 mm or more, or about 5 mm to about 100 mm. In specific embodiments, the conduit overlap length is about 15 mm to about 100 mm. In more specific embodiments, the conduit overlap length is about 20 mm to about 50 mm, e.g., about 30 mm. In some instances, the first conduit is longer than the second conduit and in other instances, the second conduit is longer than the first conduit. And in yet other instances, both conduits are the same length. In some embodiments, the first outlet end extends beyond the second outlet end by a suitable amount (e.g., as illustrated by l 2 in the figures, described herein as the protrusion length - e.g., of the first conduit).
  • a suitable amount e.g., as illustrated by l 2 in the figures, described herein as the protrusion length - e.g., of the first conduit.
  • the first outlet end extends beyond the second outlet end by about -0.5mm to about 1.5 mm. In more specific instances, the first outlet end extends beyond the second outlet end by about 0 mm to about 0.8 mm. In still more specific embodiments, the first outlet end extends beyond the second outlet end by about 0.1 mm to about 0.5 mm.
  • the first conduit has a first diameter (e.g., diameter of the interior surface of the first walls) and the second conduit has a second diameter (e.g., diameter of the interior surface of the second walls).
  • first diameter is any suitable diameter.
  • the first diameter is about 0.05 mm to about 3 mm.
  • the first diameter is 0.3 to 3 mm, about 0.5 mm to about 1 mm, or about 0.6 mm to about 0.9 mm.
  • the walls surrounding the first conduit have a first wall diameter of about 0.1 to about 4 mm, e.g., about 0.5 mm to about 3.8 mm. In more specific embodiments, the first wall diameter is about 0.8 mm to about 1.8 mm, or about 1 mm to about 1.5 mm. In some embodiments, the second diameter is any suitable diameter. In specific embodiments, the second diameter is about 0.1 mm to about 5 mm. In more specific embodiments, the second diameter is about 0.8 to 4 mm, about 1 mm to about 2.5 mm, about 0.8 mm to 2 mm (such as when the third conduit inside which the second conduit is positioned is present), or about 1.3 mm to 1.6 mm.
  • the conduits described herein have any suitable shape.
  • the conduits are cylindrical (e.g., oval or circular cylinders), prismatic (e.g., an octagonal prism), conical (e.g., a truncated cone), pyramidal (e.g., a truncated pyramid, such as a truncated octagonal pyramid), or the like.
  • the conduits are cylindrical (e.g., wherein the conduits and walls enclosing said conduits form needles).
  • the walls of a conduit are parallel, or within about 1 or 2 degrees of parallel (e.g., wherein the conduit forms a cylinder or prism).
  • the walls of a conduit are not parallel (e.g., wherein the diameter is wider at the inlet end than the outlet end, such as when the conduit forms a cone (e.g., truncated cone) or pyramid (e.g., truncated pyramid)).
  • the walls of a conduit are within about 15 degrees of parallel, or within about 10 degrees of parallel.
  • the walls of a conduit are within about 5 degrees of parallel (e.g., within about 3 degrees or 2 degrees of parallel).
  • conical or pyramidal conduits are utilized.
  • the diameters for conduits not having parallel walls refer to the average width or diameter of said conduit.
  • the angle of the cone or pyramid is about 15 degrees or less, or about 10 degrees or less. In specific embodiments, the angle of the cone or pyramid is about 5 degrees or less (e.g., about 3 degrees or less).
  • the distance between the exterior surface of the first wall and the interior surface of the second wall is any suitable distance. In some embodiments, the distance is on average less than 0.5 mm. In specific embodiments, the distance between the exterior surface of the first wall and the interior surface of the second wall is on average less than 0.3 mm. In more specific embodiments, the distance is on average about 0.01 mm to about 0.3 mm. In still more specific embodiments, the distance is on average about 0.05 mm to about 0.3 mm.
  • a nozzle component comprising a ratio of the conduit overlap length (e.g., as illustrated by l ⁇ -to-second diameter (e.g., as illustrated by d 2 ) of at least 5.
  • the ratio is about 10 or more.
  • the ratio is about 13 or more.
  • the ratio is about 15 or more, e.g., about 17 or more.
  • the ratio is about 18 or more, e.g., about 19.
  • a nozzle component comprising a ratio of the average distance between the exterior surface of the first wall and the interior surface of the second wall (also described herein as the conduit gap, and, e.g., illustrated in the figures by d 4 ) to the second diameter (e.g., illustrated in the figures as d 2 ) of less than 0.25, e.g., about 0.2 or less.
  • the ratio of the conduit gap-to-second diameter is less than 0.15.
  • the ratio is less than 0.1.
  • the ratio is about 0.05 or less, e.g., about 0.04.
  • a nozzle component comprising a ratio of the protrusion length of the first conduit (e.g., as illustrated by 12 in the figures)-to-second diameter (e.g., as illustrated by d2 in the figures) of less than 1. In specific embodiments, the ratio is less than 0.5. In more specific embodiments, the ratio is about 0.3 or less.
  • a multi-nozzle configuration comprising a ratio of the distance between two adjacent nozzles-to-second diameter (e.g., as illustrated by d 2 in the figures) of about 0.5 to about 50.
  • the ratio is about 0.5 to about 25, or about 0.5 to about 10, e.g., about 1 to about 5.
  • the ratio is about 1.
  • the ratio is about 5.
  • a nozzle provided herein comprises a first conduit that is fluidly connected (e.g., via the inlet or supply end) to a first supply chamber, the first supply chamber configured to provide liquid polymer (e.g., polymer melt or polymer solution) to the first conduit.
  • a nozzle provided herein comprises a second conduit that is fluidly connected (e.g., via the inlet or supply end thereof) to a second supply chamber, the second supply chamber configured to provide pressurized (or high velocity) air to the second conduit.
  • the second supply chamber is a pressurized air tank, an air pump, a chamber containing a fan, or the like.
  • the first and second supply chambers are present in a manifold described in more detail herein.
  • a nozzle component described herein is configured to receive a voltage (e.g., sufficient to produce an electric field strong enough to overcome the surface tension of a liquid polymer - e.g., a polymer solution or polymer melt).
  • a nozzle, or an electrospinning apparatus comprising a nozzle, the nozzle comprising:
  • a second conduit the second conduit being enclosed along the length of the conduit by a second wall having an interior surface, the second conduit having a second inlet (or supply) end and a second outlet end, and the second conduit having a second diameter (e.g., defined by the diameter of the interior surface of the second walls); the first and second conduit having a conduit overlap length, wherein the first conduit is positioned inside the second conduit, the exterior surface of the first wall and the interior surface of the second wall being separated by a conduit gap, the first outlet end protruding beyond the second outlet end by a protrusion length, and wherein:
  • the ratio of the conduit overlap length-to-second diameter is about 10 or more (e.g., about 13 or more, or about 18 or more),
  • the ratio of the average conduit gap-to-second diameter about 0.2 or less (e.g., about 0.1 or less, or about 0.05 or less), and/or
  • the ratio of the protrusion length-to-second diameter is about 0.3 or less.
  • a nozzle, or an electrospinning apparatus comprising a nozzle, the nozzle comprising:
  • an inner conduit the inner conduit being enclosed along the length of the conduit by an inner wall having an interior and an exterior surface (e.g., the interior surface facing the inner conduit and at least a portion of the exterior surface facing the outer conduit), the inner conduit having an inner conduit inlet (or supply) end and an inner conduit outlet end, and the inner conduit having an inner conduit diameter (e.g., defined by the average diameter of the interior surface of the inner walls); and
  • an outer conduit the outer conduit being enclosed along the length of the conduit by an outer wall having an interior surface, the outer conduit having an outer conduit inlet (or supply) end and an outer conduit outlet end, and the outer conduit having an outer conduit diameter (e.g., defined by the average diameter of the interior surface of the outer walls); the inner and outer conduit having a conduit overlap length, wherein the inner conduit is positioned inside the outer conduit (e.g., with optional additional inner conduits positioned inside the inner conduit), the exterior surface of the inner wall and the interior surface of the outer wall being separated by a conduit gap, the inner conduit outlet end protruding beyond the outer conduit outlet end by a protrusion length, and wherein:
  • the ratio of the conduit overlap length-to-outer conduit diameter is about 10 or more (e.g., about 13 or more, or about 18 or more),
  • the ratio of the average conduit gap-to-outer conduit diameter about 0.2 or less (e.g., about 0.1 or less, or about 0.05 or less), and/or
  • the ratio of the inner conduit protrusion length-to -outer conduit diameter is about 0.3 or less.
  • an electrospinning apparatus (or nozzle) provided herein comprises a nozzle having a first (or inner) conduit that is fluidly connected (e.g., via the inlet or supply end) to a first supply chamber, the first supply chamber configured to provide liquid polymer (e.g., polymer melt or polymer solution) to the first conduit.
  • an electrospinning apparatus provided herein comprises a nozzle having a second (or outer) conduit that is fluidly connected (e.g., via the inlet or supply end thereof) to a second supply chamber, the second supply chamber configured to provide pressurized (or high velocity) air to the second conduit.
  • the second supply chamber is a pressurized air tank, an air pump, a chamber containing a fan, or the like.
  • an apparatus provided herein comprises a power source configured to provide a voltage to the nozzle component.
  • an apparatus provided herein comprises a grounded collector (e.g., for collecting nanofibers produced by the electrospinning apparatus).
  • the ratio of the conduit overlap length-to-outer conduit diameter is about 10 or more (e.g., about 13 or more, or about 18 or more). In further or alternative specific embodiments, the ratio of the average conduit gap-to-outer conduit diameter about 0.2 or less (e.g., about 0.1 or less, or about 0.05 or less). In further or alternative specific embodiments, the ratio of the inner conduit protrusion length-to-outer conduit diameter is about 0.3 or less.
  • the ratio of the conduit overlap length-to-outer conduit diameter is about 10 or more (e.g., about 13 or more, or about 18 or more) and the ratio of the average conduit gap-to-outer conduit diameter about 0.2 or less (e.g., about 0.1 or less, or about 0.05 or less).
  • the ratio of the conduit overlap length-to-outer conduit diameter is about 10 or more (e.g., about 13 or more, or about 18 or more), the ratio of the average conduit gap-to-outer conduit diameter about 0.2 or less (e.g., about 0.1 or less, or about 0.05 or less), and the ratio of the inner conduit protrusion length-to-outer conduit diameter is about 0.3 or less.
  • a nozzle (e.g., multi-nozzle) system for producing nanofibers comprising a manifold comprising a plurality of supply chambers and at least one (e.g., a plurality of) electrospinning nozzles (e.g., needle apparatuses).
  • a system comprising a first manifold supply chamber, a second manifold supply chamber, a first conduit (e.g., needle) in fluid contact with the first manifold supply chamber, and a second conduit (e.g., needle) in fluid contact with the second supply chamber.
  • the first conduit e.g., needle
  • the second conduit e.g., needle
  • the first conduit (e.g., needle) and the second conduit are arranged (e.g., concentrically arranged) about a common axis (e.g., within 5 degrees of the common axis).
  • the second conduit e.g., needle
  • a third conduit e.g., needle
  • conduits provided herein are enclosed conduits comprising an inlet end and an outlet end and an enclosing wall that surrounds the conduit.
  • the inlet end is opposite the outlet end.
  • a needle and other "straw-like" structures are examples of enclosed conduits comprising an inlet end and an outlet end and an enclosing wall that surrounds the conduit.
  • Embodiments described herein for "needle" structures are intended to also provide more general disclosure for enclosed conduits.
  • a multi-nozzle system described herein comprises a manifold comprising (i) a first manifold inlet in fluid contact with a first manifold supply chamber, and (ii) a second manifold inlet in fluid contact with a second manifold supply chamber.
  • a multi-nozzle system comprising a plurality of nozzles described herein (e.g., coaxial nozzle (e.g., needle) apparatuses (e.g., wherein the coaxial nozzle apparatus comprises a plurality of coaxially aligned and concentrically arranged conduits)).
  • each nozzle component (e.g., coaxial needle apparatus) comprises a first conduit (e.g., needle) comprising a first supply end and a first outlet end (e.g., the first supply end being in fluid contact with the first manifold supply chamber - either directly or via an intermediary structure).
  • each nozzle component (e.g., coaxial needle apparatus) comprises a second conduit (e.g., needle) comprising a second supply end and a second outlet end (e.g., the second supply end being in fluid contact with the second manifold supply manifold - either directly or via an intermediary structure).
  • first conduit and second conduit are aligned along a common axis (e.g., within 25% of the diameter of the outer needle and within 5 or 10 degrees of the common axis), and the first conduit (e.g., needle) is positioned inside the second conduit (e.g., needle) for at least a portion of the length of the first conduit (e.g., needle).
  • the manifold further comprises a third inlet in fluid contact with a third supply chamber.
  • each of the nozzle components e.g., coaxial needle apparatuses
  • each of the nozzle components further comprises a third conduit (e.g., needle) comprising a third supply end and a third outlet end.
  • the third supply end is in fluid contact with the third manifold supply chamber.
  • first, second, and third conduits are aligned along a common axis, the first conduit (e.g., needle) being positioned inside the second conduit (e.g., needle) for at least a portion of the length of the first conduit (e.g., needle), and the second conduit (e.g., needle) being positioned inside the third conduit (e.g., needle) for at least a portion of the length of the second conduit (e.g., needle).
  • a system provided herein comprises a stock reservoir (e.g., a syringe) in fluid connection with at least one manifold inlet (e.g., an inlet in fluid contact with the supply chamber that is in fluid contact with the inlet of the first or inner conduit (e.g., needle)).
  • the system comprises a pump, the pump configured to pump fluid from a stock reservoir through the at least one manifold inlet and into a manifold supply chamber (e.g., an inlet in fluid contact with the supply chamber that is in fluid contact with the inlet of the second, third, or outer (e.g., outermost) conduit (e.g., needle)).
  • a system configured to provide compressed / pressurized gas (e.g., air) to at least one manifold inlet (e.g., that leads to the outer conduit (e.g., needle) of a nozzle component (e.g., needle apparatus)).
  • the system comprises (a) an air pump connected to a manifold inlet; and/or (b) a high-pressure gas (e.g., air) reservoir (e.g., a gas tank) connected to at least one manifold inlet.
  • a system provided herein comprises a plurality of nozzle component (e.g., coaxial needle apparatuses), each nozzle component (e.g., coaxial needle apparatus) comprising at least two conduits (e.g., at least two needles), with one conduit arranged inside the other conduit (e.g., wherein the conduits are concentrically arranged).
  • the conduits e.g., coaxial needles
  • the concentric conduits e.g., needles of a coaxial needle apparatus
  • the concentric conduits e.g., needles of a coaxial needle apparatus
  • the concentric conduits (e.g., needles of a coaxial needle apparatus) provided herein are aligned within 10 degrees of a common axis. In still more specific embodiments, the concentric conduits (e.g., needles of a coaxial needle apparatus) provided herein are aligned within 5 degrees of a common axis. In yet more specific embodiments, the concentric conduits (e.g., needles of a coaxial needle apparatus) provided herein are aligned within 2 degrees of a common axis. In preferred embodiments, the concentric conduits (e.g., needles of a coaxial needle apparatus) provided herein are aligned within 1 degrees of a common axis.
  • each conduit is arranged around a longitudinal axis.
  • conduits (e.g., needles) of a nozzle component (e.g., coaxial needle) provided herein are aligned around a common (longitudinal) axis.
  • axes of each of the conduits (e.g., needles) of a nozzle component (e.g., coaxial needle) are aligned within 500 microns of one another.
  • axes of each of the conduits (e.g., needles) of a nozzle component (e.g., coaxial needle) are aligned within 250 microns of one another.
  • axes of each of the conduits (e.g., needles) of a nozzle component (e.g., coaxial needle) are aligned within 100 microns of one another. In specific embodiments, axes of each of the conduits (e.g., needles) of a nozzle component (e.g., coaxial needle) are aligned within 50 microns of one another. In specific embodiments, axes of each of the conduits (e.g., needles) of a nozzle component (e.g., coaxial needle) are aligned within 20 microns of one another.
  • the first (or inner) conduit e.g., needle
  • the second (or outer) conduit e.g., needle
  • the first (e.g., innermost) conduit e.g., needle
  • the second (e.g., intermediate inner) conduit e.g., needle
  • the third (e.g., outer or outermost) conduit e.g., needle
  • the first conduit e.g., needle
  • the second conduit e.g., needle
  • the second conduit e.g., needle
  • the third conduit e.g., needle
  • the third conduit e.g., needle
  • the third conduit has a (inner) diameter of 1.5 mm to 4 mm.
  • the third conduit e.g., needle
  • the third conduit has a (inner) diameter of 2 mm to 3 mm (or about 9-12 gauge).
  • the third conduit e.g., needle
  • the second conduit e.g., needle
  • the second conduit has a (inner) diameter of about 0.8 to about 4 mm (or about 7-18 gauge).
  • the second conduit e.g., needle
  • the second conduit has a (inner) diameter of 0.8 mm to 2 mm (or about 13-18 gauge), such as when the third conduit (e.g., needle) is present.
  • the second conduit e.g., needle
  • the second conduit e.g., needle
  • the second conduit has an outer diameter (e.g., outer diameter of a wall enclosing the second conduit, such as the outer wall of a needle) of 1 mm to 2.4 mm (or about 13-18 gauge), such as when the third conduit (e.g., needle) is present.
  • the second conduit e.g., needle
  • the first conduit has a (inner) diameter of about 0.3 to about 3 mm (or about 9-24 gauge). In specific embodiments, the first conduit (e.g., needle) has a (inner) diameter of about 0.5 mm to about 1.2 mm (or about 16-21 gauge). In specific embodiments, the first conduit (e.g., needle) has a (inner) diameter of 0.5 mm to 1 mm (or about 17-21 gauge). In specific embodiments, the first conduit (e.g., needle) has a (inner) diameter of 0.6 mm to 0.9 mm (or about 18-19 gauge).
  • the first conduit e.g., needle
  • the first conduit has an outer diameter (e.g., outer diameter of a wall enclosing the first conduit, such as the outer wall of a needle) of 0.5 mm to 3.8 mm (or about 9-24 gauge).
  • the first conduit e.g., needle
  • the first conduit has an outer diameter of about 0.8 mm to about 1.7 mm (or about 16-21 gauge).
  • the first conduit e.g., needle
  • the first conduit e.g., needle
  • the first conduit has an outer diameter of 1 mm to 1.3 mm (or about 18-19 gauge).
  • nozzle component e.g., coaxial needle apparatuses
  • nozzle component e.g., coaxial needle apparatuses
  • nozzle component e.g., coaxial needle apparatuses
  • nozzle component e.g., coaxial needle apparatuses
  • each of the conduits (e.g., needles) of the nozzle component terminate within 5 mm of one another (e.g., 113 of FIG. 1 or ⁇ of FIG. 3 is -5 mm to 5 mm).
  • each of the conduits (e.g., needles) of the nozzle component (e.g., coaxial needle apparatus) terminate within 1 mm of one another. In more specific embodiments, each of the conduits (e.g., needles) of the nozzle apparatus (e.g., coaxial needle apparatus) terminate within 500 micron of one another. In still more specific embodiments, each of the conduits (e.g., needles) of the nozzle apparatus (e.g., coaxial needle apparatus) terminate within 100 micron of one another.
  • a system provided herein comprises a heater.
  • the heater is configured to heat one or more supply manifold, one or more nozzle component (e.g., coaxial needle apparatus), or a combination thereof.
  • the heater or an additional heater (furnace) is configured to thermally treat the spun nanofibers.
  • a system provided herein comprises a nanofiber collection surface (e.g., a grounded collection surface) in operable proximity to the terminal ends of the nozzle component(s) (e.g., coaxial needle apparatuses).
  • the nanofiber collection surface is a continuous conveyor collector.
  • a power supply configured to provide voltage to the nozzle component (e.g., to provide the electric force sufficient to electrospin nanofibers from a polymer liquid - e.g., polymer solution or melt).
  • the voltage supplied to the nozzle component is any suitable voltage, such as about 10 kV to about 50 kV. In more specific embodiments, the voltage supplied is about 20 kV to about 30 kV, e.g., about 25 kV.
  • a system provided herein comprises at least one manifold supply chamber containing therein a liquid polymer composition (i.e., a fluid stock for electrospinning).
  • the liquid polymer composition is a composition comprising a polymer and a solvent (e.g., water, dimethylformamide (DMF), a hydrocarbon, or the like).
  • the liquid polymer composition further comprises metal precursor (e.g., metal ions (e.g., from disassociated metal salt), metal salt, such as metal acetate, metal nitrate, metal halide, or the like), nanoparticles (e.g., metal, metalloid, metal oxide, ceramic, or the like nanoparticles), or the like.
  • the liquid polymer composition comprises a polymer melt (either alone or in combination with another agent).
  • the liquid polymer has any suitable viscosity, such as about 10 mPa.s to about 10,000 mPa.s (at 1/s, 20 °C), or about 100 mPa.s to about 5000 mPa.s (at 1/s, 20 °C), or about 1500 mPa.s (at 1/s, 20 °C).
  • liquid polymer is provided to the nozzle at any suitable flow rate.
  • the flow rate is about 0.01 to about 0.5 mL/min. In more specific embodiments, the flow rate is about 0.05 to about 0.25 mL/min.
  • the flow rate is about 0.075 mL/min to about 0.125 mL/min, e.g., about 0.1 mL/min.
  • at least one manifold supply chamber contains therein a fluid consisting essentially of gas (e.g., air).
  • the nozzle velocity of the gas is any suitable velocity, e.g., about 0.1 m/s or more. In specific embodiments, the nozzle velocity of the gas is about 1 m/s to about 300 m/s.
  • the pressure of the gas provided is any suitable pressure, such as about 2 psi to 20 psi. In specific embodiments, the pressure is about 5 psi to about 15 psi. In more specific embodiments, the pressure is about 8 to about 12 psi, e.g., about 10 psi.
  • a process comprising (i) providing into at least one manifold inlet of a system described herein a liquid polymer composition; and (ii) providing into at least one other manifold inlet of a system described herein a high pressure gas (e.g., air).
  • a high pressure gas e.g., air
  • processes for cleaning one or more needle apparatus described herein the process comprising providing into at least one manifold inlet a compressed / high pressure gas (e.g., air). In some instances, this gas removes polymer build-up on the needle apparatus.
  • a process for producing nanofibers comprising providing a nozzle component described herein, providing a liquid polymer (e.g., as described herein) to a first (or inner) conduit of said nozzle component, providing a pressurized and/or high speed gas to a second (or outer) conduit of said nozzle component, and providing a voltage to said nozzle component.
  • Suitable nozzle systems include any nozzle system described herein.
  • a collector e.g., grounded collector
  • the liquid polymer and gas are provided to the nozzle component via a manifold system described herein.
  • the nozzle component comprises:
  • a second (or outer) conduit the second conduit being enclosed along the length of the conduit by a second wall having an interior surface, the second conduit having a second inlet (or supply) end and a second outlet end, and the second conduit having a second diameter defined by the diameter of the interior surface of the second walls.
  • the first and second conduit having a conduit overlap length.
  • the first conduit is positioned inside the second conduit, the exterior surface of the first wall and the interior surface of the second wall being separated by a conduit gap.
  • the first outlet end protruding beyond the second outlet end by a protrusion length.
  • the second conduit has a second diameter (e.g., diameter of the interior surface of the second walls).
  • nozzle components useful in such processes include those having any characteristic described herein, such as wherein (i) the ratio of the conduit overlap length-to-second diameter is about 10 or more (e.g., about 13 or more, or about 18 or more), (ii) the ratio of the average conduit gap-to-second diameter about 0.2 or less (e.g., about 0.1 or less, or about 0.05 or less), and/or (iii) the ratio of the protrusion length-to-second diameter is about 0.3 or less.
  • any disclosure in this description of a specific value described herein includes a disclosure of a value “about” equal to that value (e.g., “1” includes a disclosure of "about 1”).
  • any disclosure of an approximate value in this description also includes disclosure of a value equal to that value (e.g., "about 1” includes a disclosure of "1”).
  • FIG. 1 illustrates a two-needle electrospinning system provided herein.
  • FIG. 2 illustrates a three-needle electrospinning system provided herein.
  • FIG. 3 illustrates an alternate configuration of a two-needle electrospinning system provided herein.
  • FIG. 4 illustrates a stacked bank electrospinning system provided herein.
  • FIG. 5 illustrates exemplary polymer nanofibers prepared using a single needle apparatus (Panel A) and using needle apparatuses described herein with a liquid polymer composition through an inner needle and gas assistance through an outer needle (Panel B).
  • FIG. 6 illustrates exemplary polymer composite nanofibers prepared using a single needle apparatus (Panel A) and using needle apparatuses described herein with a liquid polymer composition through an inner needle and gas assistance through an outer needle (Panel B).
  • FIG. 7 illustrates a slightly offset coaxial needle apparatus provided herein.
  • FIG. 8 illustrates exemplary electrospinning nozzle apparatuses provided herein, and cross- sections thereof.
  • FIG. 9 illustrates an exemplary coaxial needle electrospinning apparatus provided herein.
  • nozzle apparatuses e.g., nozzle apparatuses and components, such as needle apparatuses
  • processes such as for producing nanofibers.
  • nozzle components e.g., of an electrospinning system
  • an electrospinning system such as for the production (e.g., mass production) of nanofibers.
  • a stacked multi-nozzle system for the mass production of nanofibers provided herein is a gas- assisted electrospinning (GAES) nozzle system has several nozzle components (e.g., coaxial needle apparatuses (e.g., two-needle apparatuses, three-needle apparatuses, four-needle apparatuses, or the like)), which are configured with a manifold system in a "stacked" format (e.g., as illustrated in an exemplary embodiments in FIG. 4).
  • coaxial needle apparatuses e.g., two-needle apparatuses, three-needle apparatuses, four-needle apparatuses, or the like
  • a liquid polymer composition (either pure polymer melt, or a combination of polymer and other agents, such as solvents, metal precursors, or the like) is supplied to the inner conduit (e.g., needle) of the stacked nozzles; and pressurized (e.g., compressed) or high velocity gas (e.g., air) is supplied to the outer conduit (e.g., needle).
  • pressurized e.g., compressed
  • high velocity gas e.g., air
  • such systems can produce core/shell type nanofibers using this same configuration, supplying another polymer solution to the outer conduit (e.g., needle) instead of supplying gas.
  • a third conduit e.g., needle
  • such systems can produce core/ shell type nanofibers with GAES process. Furthermore, we can easily add more pieces for the various spinning process.
  • the inner conduit e.g., needle
  • liquid polymer e.g., needle
  • the nozzle components can be cleaned by applying compressed air to the polymer supply conduit (e.g., inner conduit (e.g., needle)), which offers a facile self-cleaning mechanism.
  • the polymer supply conduit e.g., inner conduit (e.g., needle)
  • Electrospinning is a process for producing fine fibers with diameters ranging from micron scale to nano scale through the action of electrical forces.
  • the surface tension of polymer melt or solution is overcome by the electrical force applied to it, a charged jet is ejected from the surface.
  • the jet initially extends in a straight line, then undergoes a whipping motion during the flight from nozzle to collector.
  • fibers are collected on a grounded mesh or plate in the form of a nonwoven web with high surface area.
  • fiber mats that prepared have a high surface area to mass ratio, and thus has great potential for filtration, biomedical, and sensing applications.
  • nanofibers provided using the systems, apparatuses, components, or processes described herein have any desired diameter, such as less than 2 micron, 50 nm to 1500 nm, 200 nm to 1000 nm, or the like.
  • FIG. 1 illustrates a non-limiting exemplary system provided herein.
  • the (manifold) system 100 comprises a manifold housing 117.
  • the system or manifold 100 comprises (i) a first manifold inlet 101 in fluid contact with a first manifold supply chamber 102, and (ii) a second manifold inlet 103 in fluid contact with a second manifold supply chamber 104.
  • the system comprises a plurality of nozzle components (e.g., coaxial needle apparatuses) 105.
  • Panel IB illustrates a nozzle component (e.g., needle apparatus) proved herein separate from the manifold of a system described herein.
  • nozzle component e.g., coaxial needle apparatuses
  • first conduit e.g., needle
  • second conduit e.g., needle
  • the first conduit supply end is fluidly connected to the first supply chamber via a first supply component 119 (as illustrated in FIG. 1, such supply chamber has two components 119 and 119a).
  • the second conduit supply end is fluidly connected to the second supply chamber via a second supply component 120.
  • the first conduit (e.g., needle) and second conduit (e.g., needle) are aligned or arranged along or around a common axis 112.
  • Panel 1C illustrates a cutout 116 of a portion of the nozzle component (e.g., needle apparatus), illustrating a common axis along and around which the first and second conduits (e.g., needles) may be aligned or arranged (the common axis may constitute the central longitudinal axis of either or both of the first and second conduits or needles).
  • the first conduit (e.g., needle) 106 is positioned inside the second conduit (e.g., needle) 109 for at least a portion of the length of the first conduit (e.g., needle) 118 (l 1 ).
  • the first conduit comprises a first wall 121 (e.g., that encloses the conduit longitudinally) and the second conduit comprises a second wall 122 (e.g., that encloses the conduit longitudinally).
  • the first conduit protrudes 106b a certain distance 113 (l 2 ) beyond the second conduit outlet.
  • a voltage is supplied to the needle component 105 (e.g., voltage sufficient to overcome the surface tension of a liquid polymer composition - such as 5 kV to 100 kV, e.g., 8 kV to 40 kV, or 20 kV to 30 kV) to produce a jet 114, which is collected on a collection surface (not shown) as a nanofiber.
  • a polymer composition (fluid stock) is optionally provided to one or more manifold inlet by any suitable device, e.g., by a syringe or a pump.
  • a (pressurized / compressed) gas is optionally provided to one or more manifold inlet by any suitable device, e.g., a gas canister, pump, or the like.
  • FIG. 2 illustrates another non-limiting exemplary system provided herein.
  • the system comprises a manifold.
  • the system or manifold comprises (i) a first manifold inlet in fluid contact with a first manifold supply chamber 201, (ii) a second manifold inlet in fluid contact with a second manifold supply chamber 202, and (iii) a third manifold inlet in fluid contact with a third manifold supply chamber 203.
  • the system is configured to receive a fluid polymer composition into any manifold supply chamber (e.g., as shown in FIG.
  • the system is configured to receive a gas into any manifold supply chamber (e.g., as shown in FIG. 2 - in the third manifold supply chamber 203) via any suitable device 206 (e.g., via gas tank or pump).
  • the system comprises a plurality of nozzle components (e.g., coaxial needle apparatuses) 204.
  • nozzle components e.g., coaxial needle apparatuses
  • first conduit e.g., needle
  • second conduit e.g., needle
  • third conduit e.g., needle
  • first conduit and second conduit are aligned along a common axis 112.
  • 207 illustrates a cross- sectional view of an exemplary tri-conduit nozzle component (e.g., three-needle coaxial needle apparatus), with the third conduit (e.g., needle) 208 surrounding the second conduit (e.g., needle) 209, which in turn surrounds the first conduit (e.g., needle) 210.
  • the first conduit (e.g., needle) 210 is positioned inside the second conduit (e.g., needle) 209 for at least a portion of the length of the first conduit (e.g., needle), and the second conduit (e.g., needle) 209 is positioned inside the third conduit (e.g., needle) 208 for at least a portion of the length of the second conduit (e.g., needle).
  • a voltage is supplied 211 to the nozzle component (e.g., needle apparatus) 204 (e.g., voltage sufficient to overcome the surface tension of a liquid polymer or polymer solution) to produce a jet, which is collected on a collection surface 212 as a nanofiber.
  • Systems described herein optionally comprise a single manifold housing that contains the first, second, and any additional supply chambers (e.g., as illustrated in FIG. 1 and FIG. 2).
  • systems described herein comprise separate manifold systems, e.g., wherein a system comprises a first manifold housing a first supply chamber, with a first manifold inlet in fluid contact with a first manifold supply chamber and a second manifold housing a second supply chamber, with a second manifold inlet in fluid contact with a second manifold supply chamber.
  • FIG. 3 illustrates a section of a non-limiting exemplary system provided herein.
  • the system comprises a manifold 100.
  • the manifold 100 comprises (i) a first manifold supply chamber 102, and (ii) a second manifold supply chamber 104.
  • the system comprises a plurality of multi-conduit nozzle components (e.g., coaxial needle apparatuses) 105.
  • multi-conduit nozzle components e.g., coaxial needle apparatuses
  • a portion of the second conduit is removed 312 to provide display of the first conduit position inside the second conduit.
  • the first conduit is positioned inside the second conduit.
  • first and second conduits are enclosed, with the exception of the supply and outlet ends.
  • first conduit e.g., needle
  • second conduit e.g., needle
  • the system is configured to allow a voltage to be supplied to the needle apparatus 105 (e.g., voltage sufficient to overcome the surface tension of a liquid polymer or polymer solution) to produce a jet, which is collected on a collection surface (not shown) as a nanofiber.
  • the first conduit e.g., needle
  • the second conduit e.g., needle
  • the second conduit has any suitable diameter 310 (e.g., inner diameter (d 2 )), such as a diameter described herein.
  • a nozzle apparatus comprising a first conduit and a second conduit, the first conduit arranged inside the second conduit.
  • the nozzle apparatus comprises (i) a nozzle component comprising the first conduit and the second conduit, and (ii) an optional supply component (e.g., that is operably and fluidly connected to the nozzle component and a supply source, such as a manifold system described herein).
  • a nozzle apparatus comprises (i) a first conduit (e.g., needle) 106 comprising a portion that has substantially parallel (e.g., parallel, or within 15 degrees, within 10 degrees, or within 5 degrees of parallel) walls 303 and (ii) an optional first supply component 307 that has non-parallel walls 308 (e.g., substantially non- parallel walls, or greater than 15 degrees, greater than 10 degrees, or greater than 5 degree from parallel).
  • a first conduit e.g., needle
  • substantially parallel e.g., parallel, or within 15 degrees, within 10 degrees, or within 5 degrees of parallel
  • an optional first supply component 307 that has non-parallel walls 308 (e.g., substantially non- parallel walls, or greater than 15 degrees, greater than 10 degrees, or greater than 5 degree from parallel).
  • the nozzle apparatus comprises (i) a second conduit (e.g., needle) comprising a portion that has substantially parallel walls 302 (e.g., parallel - as shown, or within 15 degrees, within 10 degrees, or within 5 degrees of parallel), and (ii) an optional second supply component 304 that has non-parallel walls 301 (e.g., substantially non-parallel walls, or greater than 15 degrees, greater than 10 degrees, or greater than 5 degree from parallel - e.g., as illustrated by the angle 305).
  • the walls of the outer conduit of the nozzle component e.g., needle, such as the second needle 109 as illustrated in FIG.
  • the nozzle apparatus are aligned (e.g., parallel - as shown, or within 15 degrees, within 10 degrees, or within 5 degrees of parallel) (e.g., and are aligned (e.g., parallel - as shown, or within 15 degrees, within 10 degrees, or within 5 degrees of parallel) with the walls of the inner conduit(s) (e.g., needle(s), such as the first needle 106)) for at least a portion of the length of the nozzle (e.g., needle) 306 (l 1 ) apparatus.
  • the length of l 1 is long enough to provide high performance and/or highly uniform nanofibers.
  • the length of l 1 is long enough to provide a system suitable for high throughput production of nanofibers.
  • the first or inner conduit extends beyond (or protrudes beyond) the end of the second or outer conduit 311 (l 2 ).
  • the outer surface of the wall enclosing the first (inner) conduit and the inner surface of the wall enclosing the second (outer) conduit are set off by a certain distance 313. In some embodiments, the average of this distance is the conduit gap (d 4 ).
  • the ratio of the length l 1 to the diameter of the inner conduit is at least 20. In more specific embodiments, ratio is at least 25, at least 30, at least 40, at least 50, or the like. In further or additional specific embodiments, the ratio of l 1 to the diameter of the outer conduit (e.g., needle) (e.g., the second conduit 109 in FIG. 3 having a diameter d 2 ) is at least 10, at least 20, at least 25, at least 30, at least 40, at least 50, or the like.
  • FIG. 8 illustrates exemplary electrospinning nozzle apparatuses 800 and 830 provided herein. Illustrated by both nozzle components 800 and 830 some embodiments, the nozzle apparatus comprises a nozzle component comprising a first conduit, the first conduit being enclosed along the length of the conduit by a first wall 801 and 831 having an interior and an exterior surface, and the first conduit having a first inlet (or supply) end 802 and 832 (e.g., fluidly connected to a first supply chamber and configured to receive a liquid polymer - such as a liquid polymer composition) and a first outlet end 803 and 833.
  • a nozzle component comprising a first conduit, the first conduit being enclosed along the length of the conduit by a first wall 801 and 831 having an interior and an exterior surface, and the first conduit having a first inlet (or supply) end 802 and 832 (e.g., fluidly connected to a first supply chamber and configured to receive a liquid polymer - such as a liquid polymer composition) and a
  • the first conduit has a first diameter 804 and 834 (e.g., the average diameter as measured to the inner surface of the wall enclosing the conduit (d 1 ) or the average diameter as measured to the outer surface of the wall enclosing the conduit (d 1 )).
  • the nozzle component comprising a second conduit, the second conduit being enclosed along the length of the conduit by a second wall 805 and 835 having an interior and an exterior surface, and the second conduit having a second inlet (or supply) end 806 and 836 (e.g., fluidly connected to a second supply chamber and configured to receive a gas - such as a high velocity or pressurized gas (e.g., air)) and a second outlet end 807 and 837.
  • a gas - such as a high velocity or pressurized gas (e.g., air)
  • the second inlet (supply) end 806 and 836 are connected to a supply chamber (e.g., in a manifold described herein - e.g., comprising the second supply chamber and, optionally, the first supply chamber).
  • the second inlet (supply) end 806 and 836 are connected to the second supply chamber via a supply component.
  • FIG. 8 illustrates an exemplary supply component comprising a connection supply component (e.g., tube) 813 and 843 that fluidly connects 814 and 844 the supply chamber (not shown) to an inlet supply component 815 and 845, which is fluidly connected to the inlet end of the conduit.
  • the figure illustrates such a configuration for the outer conduit, but such a configuration is also contemplated for the inner and any intermediate conduits as well.
  • the first conduit has a first diameter 808 and 838 (e.g., the average diameter as measured to the inner surface of the wall enclosing the conduit (d 2 )).
  • the first and second conduits have any suitable shape.
  • the conduits are cylindrical (e.g., circular or elliptical), prismatic (e.g., a octagonal prism), conical (e.g., a truncated cone - e.g., as illustrated by the outer conduit 835) (e.g., circular or elliptical), pyramidal (e.g., a truncated pyramid, such as a truncated octagonal pyramid), or the like.
  • the conduits are cylindrical (e.g., wherein the conduits and walls enclosing said conduits form needles).
  • the walls of a conduit are parallel, or within about 1 or 2 degrees of parallel (e.g., wherein the conduit forms a cylinder or prism).
  • the nozzle apparatus 800 comprise a first and second conduit having parallel walls 801 and 805 (e.g., parallel to the wall on the opposite side of the conduit, e.g., as illustrated by 801a / 801b and 805a / 805b, or to a central longitudinal axis 809).
  • the walls of a conduit are not parallel (e.g., wherein the diameter is wider at the inlet end than the outlet end, such as when the conduit forms a cone (e.g., truncated cone) or pyramid (e.g., truncated pyramid)).
  • the nozzle apparatus 830 comprise a first conduit having parallel walls 831 (e.g., parallel to the wall on the opposite side of the conduit, e.g., as illustrated by 831a / 831b, or to a central longitudinal axis 839) and a second conduit having non-parallel walls 835 (e.g., not parallel or angled to the wall on the opposite side of the conduit, e.g., as illustrated by 835a / 835b, or to a central longitudinal axis 839).
  • the walls of a conduit are within about 15 degrees of parallel (e.g., as measured against the central longitudinal axis, or half of the angle between opposite sides of the wall), or within about 10 degrees of parallel.
  • the walls of a conduit are within about 5 degrees of parallel (e.g., within about 3 degrees or 2 degrees of parallel).
  • conical or pyramidal conduits are utilized.
  • the diameters for conduits not having parallel walls refer to the average width or diameter of said conduit.
  • the angle of the cone or pyramid is about 15 degrees or less (e.g., the average angle of the conduit sides/walls as measured against a central longitudinal axis or against the conduit side/wall opposite), or about 10 degrees or less.
  • the angle of the cone or pyramid is about 5 degrees or less (e.g., about 3 degrees or less).
  • the first conduit 801 and 831 and second conduit 805 and 835 having a conduit overlap length 810 and 840 (l 1 ), wherein the first conduit is positioned inside the second conduit (for at least a portion of the length of the first and/or second conduit).
  • the exterior surface of the first wall and the interior surface of the second wall are separated by a conduit gap 811 and 841 (d 4 ).
  • the first outlet end protrudes beyond the second outlet end by a protrusion length 812 and 842 (l 2 ).
  • the ratio of the conduit overlap length-to-second diameter is any suitable amount, such as an amount described herein, e.g., about 10 or more (e.g., about 13 or more, or about 18 or more).
  • the ratio of the average conduit gap-to-second diameter is any suitable amount, such as an amount described herein, e.g., about 0.2 or less (e.g., about 0.1 or less, or about 0.05 or less). In further or alternative instances, the ratio of the protrusion length-to-second diameter is any suitable amount, such as an amount described herein, e.g., about 0.3 or less.
  • FIG. 8 also illustrates cross-sections of various nozzle components provided herein 850, 860 and 870. Each comprises a first conduit 851, 861 and 871 and second conduit 854, 864, and 874. As discussed herein, in some instances, the first conduit is enclosed along the length of the conduit by a first wall 852, 862 and 872 having an interior and an exterior surface and the second conduit is enclosed along the length of the conduit by a second wall 855, 865 and 875 having an interior and an exterior surface. Generally, the first conduit has any suitable first diameter 853, 863 and 864 (d 1 ) and any suitable second diameter 856, 866, and 876 (d 2 ).
  • the cross-dimensional shape of the conduit is any suitable shape, and is optionally different at different points along the conduit.
  • the cross-sectional shape of the conduit is circular 851 / 854 and 871 / 874, elliptical, polygonal 861 / 864, or the like.
  • coaxially configured nozzles provided herein and coaxial gas assisted electrospinning comprises providing a first conduit or fluid stock along a first longitudinal axis, and providing a second conduit or gas (e.g., pressurized or high velocity gas) around a second longitudinal axis (e.g., and electrospinning the fluid stock in a process thereof).
  • a second conduit or gas e.g., pressurized or high velocity gas
  • the first and second longitudinal axes are the same.
  • the first and second longitudinal axes are different.
  • the first and second longitudinal axes are within 500 microns, within 100 microns, within 50 microns, or the like of each other.
  • the first and second longitudinal axes are aligned within 15 degrees, within 10 degrees, within 5 degrees, within 3 degrees, within 1 degree, or the like of each other.
  • FIG. 8 illustrates a cross section of a nozzle component 870 having an inner conduit 871 that is off-center (or does not share a central longitudinal axis) with an outer conduit 874.
  • the conduit gap e.g., measurement between the outer surface of the inner wall and inner surface of the outer wall
  • the smallest distance between the inner surface of the outer wall 876 and the diameter of the outer surface of the inner wall 872 is at least 10% (e.g., at least 25%, at least 50%, or any suitable percentage) of the largest distance between the inner surface of the outer wall 876 and the diameter of the outer surface of the inner wall 872.
  • FIG. 9 provides a non-limiting three dimensional illustration (with illustrative cut outs 901 and 902) of a nozzle component (e.g., coaxial needle nozzle component) 900 provided herein.
  • the needle apparatus or nozzle component
  • the needle apparatus comprises a first (inner) needle 904 comprising a first (inner) conduit 904 enclosed by a first wall 905, the first wall comprising a first wall inner surface 906, a first wall outer surface 907, a first (inner) outlet end 908, a first (inner) inlet (supply) end (e.g., configured to be in fluid contact with a first supply chamber, and/or to receive a liquid polymer), a first inner diameter 918 (d 1 ) and a first outer diameter 919 (d 1 ).
  • the needle apparatus (or nozzle component) comprises a second (outer) needle 909 comprising a second (outer) conduit 910 enclosed by a second wall 911, the first wall comprising a second wall inner surface 912, a (optional) second wall outer surface 913, a second (outer) outlet end 914, a second (outer) inlet (supply) end (e.g., configured to be in fluid contact with a second supply chamber, and/or to receive a liquid polymer or high velocity or high pressure gas (e.g., air)) a second inner diameter 920 (d 2 ) and (optionally) a second outer diameter.
  • a second inner diameter 920 d 2
  • a second outer diameter e.g., air
  • the first (inner) needle 903 is positioned inside the second needle 909 for at least a portion of the length of the first needle 915 (l 1 ). In certain instances, the first needle 903 (outlet end 908) protrudes a certain distance 916 (l 2 ) beyond the second needle 909 (outlet end 914). As discussed for other embodiments described herein, in some instances, the exterior surface of the first (inner) wall 907 and the interior surface of the second (outer) wall 912 are separated by a conduit gap 917 (d 4 ).
  • the ratio of the conduit overlap length 915 -to- second inner diameter 920 is any suitable amount, such as an amount described herein, e.g., about 10 or more (e.g., about 13 or more, or about 18 or more). In further or alternative instances, the ratio of the average conduit gap 917 -to- second inner diameter 920 is any suitable amount, such as an amount described herein, e.g., about 0.2 or less (e.g., about 0.1 or less, or about 0.05 or less). In further or alternative instances, the ratio of the protrusion length 916 -to- second inner diameter 920 is any suitable amount, such as an amount described herein, e.g., about 0.3 or less.
  • a system provided herein comprises an apparatus comprising a plurality of rows of nozzle components (e.g., coaxial needle apparatuses) (nozzles in the rows and columns may be aligned or offset - both are aligned in the examples illustrated in FIG. 4).
  • FIG. 4 illustrates two examples of such systems.
  • a (e.g., single) first manifold supply chamber e.g., having a single inlet 101 - e.g., as illustrated in the upper panel of FIG. 4) optionally feeds the first conduits (e.g., needles) of each row of nozzles (e.g., needle apparatuses).
  • a (e.g., single) second manifold supply chamber (e.g., having a single inlet 103 - e.g., as illustrated in the upper panel of FIG. 4) optionally feeds the second conduits (e.g., needles) of each row of nozzles (e.g., needle apparatuses).
  • a plurality of first manifold supply chambers, a plurality of second manifold supply chambers, or the like are optionally utilized.
  • multiple first inlets 101 may feed the first manifold supply chamber(s)
  • multiple second inlets 103 may feed the second manifold supply chamber(s) (e.g., as illustrated in the lower panel of FIG. 4).
  • conduits (e.g., needles) of a nozzle component (e.g., coaxial needle apparatus) provided herein are aligned around a common (longitudinal) axis.
  • the (longitudinal) axes of the conduits (e.g., needles) of a nozzle component (e.g., coaxial needle apparatus) provided herein are slightly offset. In specific instances, such offset is small enough that high performance and throughput characteristics of the system are retained.
  • FIG. 7 illustrates that the central logitindual axis of an inner conduit (e.g., needle) 702 may be slightly offset from the central longitudinal axis of an outer conduit (e.g., needle) 701, such as by an amount 703 (d 3 ).
  • axes of each of the conduits (e.g., needles) of a nozzle component (e.g., coaxial needle) are aligned within any suitable distance, e.g., within about 0.5 mm, within about 200 microns, or within 100 microns of one another (e.g., 100 microns > d 3 ).
  • axes of each of the conduits (e.g., needles) of a nozzle component (e.g., coaxial needle) are aligned within 50 microns of one another. In specific embodiments, axes of each of the conduits (e.g., needles) of a nozzle component (e.g., coaxial needle) are aligned within 20 microns of one another.
  • the offset is less than 0.1 of the diameter of the inner conduit (e.g., needle) (e.g., d ' Vd 1 ⁇ 0.1). In some embodiments, the offset is less than 0.05, less than 0.03, or less than 0.01 of the diameter of the inner conduit (e.g., needle).
  • Any suitable polymer is optionally utilized in systems, apparatuses, or processed described herein e.g., any electrospinnable polymer (e.g., electrospinnable as a melt or in solution).
  • Exemplary polymers suitable for use in systems, apparatuses, or processed described herein include but are not limited to polyvinyl alcohol (“PVA”), polyvinyl acetate (“PVAc”), polyethylene oxide (“PEO”), polyvinyl ether, polyvinyl pyrrolidone, polyglycolic acid, polyvinylidene difluoride (PVDF), hydroxyethylcellulose (“HEC”), ethylcellulose, cellulose ethers, polyacrylic acid, polyisocyanate, and the like.
  • the polymer is isolated from biological material.
  • the polymer is starch, chitosan, xanthan, agar, guar gum, and the like.
  • other polymers such as polyacrylonitrile (“PAN") are optionally utilized (e.g., with DMF as a solvent).
  • PAN polyacrylonitrile
  • a polyacrylate e.g., polyalkacrylate, polyacrylic acid, polyalkylalkacrylate, or the like
  • PAN polyacrylonitrile
  • a liquid polymer e.g., polymer composition
  • a polymer composition comprises solvent and/or an additional component (such as metal precursor, metal ion, nanoparticle, or the like).
  • the polymer concentration in a polymer composition provided herein is, e.g., 5- 50 wt. %.
  • the polymer concentration is below 20 wt %.
  • the polymer concentration is 2-20 wt %.
  • the polymer concentration is 8-12 wt %.
  • compressed gas is provided to a system here at any suitable pressure.
  • the gas pressure is about 0.1 to 10 kgf/cm 2 .
  • the gas is provided at a pressure of about 0.5 ⁇ 3kgf/cm 2 .
  • any suitable distance may be utilized between the nozzle and collection plate. In some instances, the distance is about 3-100 cm. In more specific instances, the distance is about 5-50 cm, or more specifically about 10 ⁇ 25cm.
  • the flow rate of the fluid stock (e.g., to each needle apparatus) is about 0.05 mL/min to 3 mL/min, or more specifically about 0.1 ⁇ 0.5.ml/min.
  • the supply components, manifold components, and nozzle components comprise any suitable material.
  • such materials are resistant to corrosion, such as plastics (e.g., polyethylene, polypropylene, etc.) or inert or semi-inert metals.
  • nozzle components (e.g., the conduit walls) provided herein comprise stainless steel, brass, bronze, or the like.
  • nozzle components (e.g., the conduit walls) provided herein comprise plastic (e.g., polyethylene), stainless steel, brass, bronze, or the like.
  • the multi-nozzle system allows for high throughput nanofiber processing.
  • the multi-nozzle system also provides for the preparation of high performance nanofibers - e.g., nanofibers having uniform structures and components.
  • such nanofibers allow for the production of nanofibers that have narrow, uniform diameters.
  • the standard deviation of nanofibers provided, or prepared according to systems and processes described, herein is less than 100% of the average diameter, less than 50% of the average diameter, less than 25% of the average diameter, or the like.
  • Polyvinyl alcohol (PVA) ( w 78,000) is charged in DI water with concentration of 8-12 wt%.
  • the prepared polymer composition is pumped into the inner channel of spinneret and compressed air gas is provided through the outer channel with the pressure of 0.5 ⁇ 3kgf/cm 2 .
  • the distance between the nozzle and collection plate is kept to 10 ⁇ 25cm, and the flow rate of 0.1-0.5. ml/min is maintained.
  • a charge of +20 to +30 kV is maintained at the needle.
  • FIG. 5 (Panel A) illustrates an SEM of PVA nanofibers prepared without gas assistance
  • (Panel B) illustrates an SEM of PVA nanofibers prepared with gas assistance. Nanofibers prepared with gas assistance showed significantly fewer bead structures in the nanofibers, as well as much higher production rates.
  • Polyvinyl alcohol (PVA) ( w 78,000) is provided and nanoparticles with the size of 20-30 nm are supplied. PVA is dissolved in DI water with concentration of 8 ⁇ 12wt%. And nanoparticles are added in the PVA solution to prepare PVA/NP composition. The weight ratio of PVA to nanoparticles is 0.5-5, and to prevent the aggregation of nanoparticles the composition is sonicated for 3 ⁇ 5hrs.
  • the prepared polymer composition is pumped into the inner channel of spinneret and compressed air gas is provided through the outer channel with the pressure of 0.5 ⁇ 3kgf/cm 2 .
  • FIG. 6 illustrates an SEM of PVA nanofibers prepared without gas assistance
  • FIG. 6 illustrates an SEM of PVA nanofibers prepared with gas assistance.
  • PVA Polyvinyl alcohol
  • metal precursor are supplied.
  • PVA is dissolved in DI water with concentration of 8 ⁇ 12wt%.
  • metal precursor is added in the PVA solution to prepare PV A/precursor aqueous composition.
  • the weight ratio of PVA to precursor is about 2:3.
  • the prepared polymer composition is pumped into the inner channel of the nozzle at a flow rate of about 0.1 mL/min (e.g., about 0.075 to about 0.12 mL/min) and compressed air gas is provided through the outer channel with the pressure of about 10 psi (e.g., about 8 psi to about 12 psi).
  • the distance between the nozzle and collection plate is kept to 20-30 cm (e.g., about 25 cm).
  • a charge of +20 to +30 kV (e.g., about +25 kV) is maintained at the needle.
  • a manifold system comprising a plurality of nozzles described was utilized to prepare polymer composite nanofibers.
  • Various nozzle configurations were utilized, such as set forth in Table 1.
  • the spinnability is measured qualitatively, with 1 being extremely poor electrospinnability
  • Table 1 illustrates that superior electrospinnability is achieved at lower values of d4/d2 (e.g., compare 5 and 8), at higher values of ll/d2 (e.g., compare 2 and 3, 4 and 5), and at lower values of 12/d2 (e.g., compare 8 and 9).

Abstract

L'invention porte sur des systèmes, sur des appareils, sur des éléments et sur des procédés d'électrofilature pour la préparation de nanofibres, lesquels comprennent des systèmes, des appareils et des procédés à débit de sortie élevé pour produire des nanofibres de hautes performances.
PCT/US2014/025699 2013-03-14 2014-03-13 Appareils et procédés d'électrofilature WO2014160045A1 (fr)

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US15/271,682 US20170009380A1 (en) 2013-03-14 2016-09-21 Multi-nozzle gas-assisted electrospinning apparatuses
US16/426,626 US20190345637A1 (en) 2013-03-14 2019-05-30 Multi-nozzle gas-assisted electrospinning apparatuses
US17/549,130 US20220098759A1 (en) 2013-03-14 2021-12-13 Multi-nozzle gas-assisted electrospinning apparatuses

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US20140353882A1 (en) 2014-12-04

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