WO2019014686A1 - Méthodes et systèmes d'électrofilage - Google Patents

Méthodes et systèmes d'électrofilage Download PDF

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Publication number
WO2019014686A1
WO2019014686A1 PCT/US2018/042354 US2018042354W WO2019014686A1 WO 2019014686 A1 WO2019014686 A1 WO 2019014686A1 US 2018042354 W US2018042354 W US 2018042354W WO 2019014686 A1 WO2019014686 A1 WO 2019014686A1
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WO
WIPO (PCT)
Prior art keywords
voltage
collector
inter
electrodes
nozzle
Prior art date
Application number
PCT/US2018/042354
Other languages
English (en)
Inventor
Paul SOLDATE
Jintu Fan
Original Assignee
Cornell University
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Filing date
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Application filed by Cornell University filed Critical Cornell University
Publication of WO2019014686A1 publication Critical patent/WO2019014686A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/04—Rotational or centrifugal casting, i.e. coating the inside of a mould by rotating the mould
    • B29C41/06—Rotational or centrifugal casting, i.e. coating the inside of a mould by rotating the mould about two or more axes
    • 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
    • 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
    • D01F6/66—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyethers

Definitions

  • the present disclosure generally relates to methods and systems for
  • the present disclosure relates to methods and systems for depositing polymer fiber structures.
  • Electrospinning is a technique often used for the production of continuous submicron diameter fibers composed of various polymers and ceramics. A typical
  • electrospinning setup utilizes a strong electric field to attract a charged viscous polymer solution from a high voltage injection site, e.g., a syringe needle, toward a grounded substrate.
  • a charged viscous polymer solution from a high voltage injection site, e.g., a syringe needle, toward a grounded substrate.
  • molecular ionization forces positive charge to its surface, causing it to bulge in a conical shape (Taylor Cone).
  • a charged jet also referred to herein as a stream
  • the viscosity of the solution maintains continuity along the flight path, ion redistribution and space charge effects make the jet increasingly unstable.
  • a charged polymer jet can be manipulated by novel substrate architectures, mechanical motion, and intermediary electric field manipulation.
  • the tradeoff between morphology control and throughput has been inversely proportional.
  • current systems do provide an ability to draw single fibers in one dimension, with relatively high throughput, the waste accumulation of random nanofibers at each point of deposition, as well as the inability to control fiber pathways in two and three-dimensions has been limiting. This has been somewhat of a deterrent for large-scale integration in an industry setting, e.g., when repeatedly drawing predetermined 2D networks of electrospun nanofibers for chemical sensors in large quantities.
  • the present disclosure provides methods and systems developed for the controlled fabrication of, for example, 2D nanofibrous geometries, by continuously accelerating the jet (linearly and/or centripetally) along the flight path. For example, this is achieved using mechanical actuation and high-voltage AC switching to manipulate the applied electric field in a continuous manner.
  • various macroscopic nanofibrous geometries can be deposited at different velocities and the alignment of their respective morphologies can be correlated.
  • the electrospinning systems of the present disclosure can continuously accelerate a charged polymer jet (linearly and/or centripetally) fast enough to obtain predetermined two and three dimensional geometries with well-aligned morphologies. This is achieved using AC switching algorithms and electronics, alongside mechanical actuation, which accommodates consistent deposition for varied level of production.
  • the methods and/or systems of the present disclosure provides a means to stretch polymer fibers toward nano-diameters while redirecting them along continuous predetermined paths to fabricate novel 2D nanofibrous geometries. For example, this is done by continuously accelerating a charged polymer jet in a two-dimensional (x-y) plane that is perpendicular to its deposition (z-axis) trajectory.
  • Figure 1 shows (A) a typical electrospinning setup. (B) Random deposition of electrospun nanofibers.
  • Figure 2 shows (A) the overall setup used in the present disclosure, including the electronics that power the system, and (B) the injection chamber (i.e., linear driving mechanism and stepper motors (1), collector plate (2), inter-electrodes (3), and syringe needle (4)).
  • injection chamber i.e., linear driving mechanism and stepper motors (1), collector plate (2), inter-electrodes (3), and syringe needle (4).
  • Figure 3 shows the injection chamber with the chosen origin between the inter- electrodes.
  • Figure 4 shows the jet being accelerated before (left) and after (right) an amplifier is pulsed.
  • Figure 5 shows a few shapes that were drawn using different permutations of the six available electrodes.
  • the star (A) is created by superimposing two triangles (B).
  • the hexagon (C) is created by pulsing centripetally. Here, a 10 Hz frequency is used.
  • Figure 6 shows (A) a spot on the order of mm collected along the z-axis. Keeping the grid at negative voltage suppresses the current and keeps the DC potential high, which was unexpectedly able to create a similar effect to Deitzel's DC electric lensing experiment. (B) The nanofibers are collected for 166 ms before switching to the next x-y coordinate on the collector by pulsing each electrode at 1 Hz. The spots are then centripetally accelerated with respect to the z-axis. [0021] Figure 7 shows the ability to transition from discrete point deposition to a more continuous deposition using higher frequencies (e.g., 15 Hz).
  • Figure 8 shows (A and B) varying the diameter by changing the electrode displacements and collector voltage.
  • Figure 9 shows (A and B) varying the diameter by changing the frequency.
  • Figure 10 shows (left) an SEM image of one segment of a 45 Hz circle with a 1 cm diameter. (Right) An SEM image of a 45 Hz circle with a diameter of 2 cm. Notice that the tangential velocity is twice as high when doubling the diameter.
  • Figure 11 shows a sequence of circles drawn one after the other. (A) After the first circle is drawn, (B) the collector plate rotates as the next is deposited.
  • Figure 12 shows the nanofibers being directly deposited onto the inter-electrodes.
  • Figure 13 shows a short list of components used in the invention.
  • Figure 14 shows the overall system. Numbers refer to the parts listed in Figure 13.
  • Figure 15 shows determining the loads for each amplifier.
  • Figure 16 shows the circuit used for the high-voltage AC amplifier. This changes the voltage/electric field to accelerate the jet. Numbers refer to the parts listed in Figure 13.
  • Figure 17 shows the amplification from the pulsed signal from the function generator (top line) and the amplifier output pulse (bottom line).
  • the actual voltage supplied to the amplifier is the middle line. This shows a 2 kHz signal, however, the amplitude, frequency, and pulse shape can be changed (e.g., sinusoidal, square, etc.).
  • Figure 18 shows how the charged jet is accelerated by the amplifier when pulses arrive.
  • (A) shows before the pulse arrives.
  • (B) shows after the pulse arrives.
  • Figure 19 shows some of the printed 2D nanofibrious geometries that are possible using several amplifiers being pulsed in a sequential manner (e.g., a hexagon, triangle, and star).
  • Figure 20 shows a CAD (computer-aided design) depiction of the emission chamber.
  • Figure 21 shows the wireframe perspective of how the electrodes (center) are driven by the stepper motors. Numbers refer to the parts lists in Figure 13.
  • Figure 22 shows the mechanism for driving each electrode back and forth/up or down.
  • Figure 23 shows an exploded view to construct the driving mechanism. Numbers refer to the parts list in Figure 13.
  • Figure 24 shows an exploded view of the driving mechanism for the
  • Figure 25 shows the dimensions required for the six electrodes to be spaced evenly (i.e., each at 60 degrees from one another).
  • Figure 26 shows how the electrode driver is attached to the bottom plate.
  • Figure 27 shows how all six electrode mechanisms are attached to the top and bottom plate.
  • the collector mechanism similar to the syringe mechanism, is also attached.
  • Figure 28 shows the assembled system, including the stepper motors, outer plates, cylinders, driving mechanisms, electrodes, and collector plate.
  • Figure 29 shows (Left) a CAD depiction of a typical electrospinning setup, including the bending instabilities as known in the art.
  • (Right) A scanning electron microscope (SEM) image of random electrospun nanofibers from a typical setup.
  • Figure 30 shows a CAD depiction of the injection chamber, as well as a spring and dashpot model of the deflected jet.
  • the positively charged polymer jet is ejected from the positively charged nozzle toward the negatively charged collector.
  • an off axis deposition radius is obtained.
  • the x-y-z origin is shown in the plane of the intermediate electrodes.
  • Figure 31 shows the electronic circuit used for each high-voltage AC amplifier.
  • a low-voltage oscillation at the grid of the vacuum tube can produce a high-voltage oscillation at the plate.
  • Figure 32 shows pulsing output capabilities of one amplifier.
  • the actual voltage supplied to the amplifier is shown in green (left image), i.e., ⁇ 5 kV.
  • a 15 Hz square wave is supplied from a function generator to the grid of one vacuum tube amplifier, which causes a high-voltage oscillation on the plate.
  • the high-voltage supply is connected to a 10 M load resistor (as seen in the circuit in Figure 31).
  • Figure 33 shows a jet is deflected before (left) and after (right) the amplifier is pulsed using the signals demonstrated in Figure 32.
  • Figure 34 shows (Left) keeping the grid at negative voltages suppresses the current and sets a DC high-voltage signal at each inter-electrode, which was unexpectedly able to create a similar effect to Deitzel's DC electric lensing experiment.
  • a spot with a diameter on the order of ⁇ 1 cm is collected along the z-axis.
  • Figure 35 shows (Left) a screenshot from a digital oscilloscope sampling three
  • Figure 36 shows a star (Left) is created by printing two triangles.
  • Figure 38 shows (left and right) varying the deposition radius by fixing the frequency and changing the voltages and distances.
  • Figure 39 shows (left and right) varying the deposition radius by changing the frequency alone.
  • Figure 40 shows an SEM comparison of the fiber orientation from the deposition patterns in Figure 39.
  • Figure 41 shows the cross-deposition of nanofibers. Each electrode is pulse 90° out of phase with its opposite, while all other inter-electrodes are held high.
  • Figure 42 shows (left and right) EM images of cross-deposited nanofibers generated in Figure 41.
  • Figure 43 shows the polymer being directly deposited onto the inter-electrodes.
  • Figure 44 shows the overall setup used in the present disclosure, including: two -
  • Figure 45 shows determination of load lines for each amplifier.
  • Figure 46 shows the injection chamber with an electrospun hexagonal geometry deposited on a printed circuit board.
  • Figure 47 shows viscosity measurements of a 10% (w/w) mixture of deionized
  • Figure 48 shows measurements of the elastic modulus (G') of PEO 10% using a frequency sweep from 1 to 10 Hz, with 20 sample points, at 25 °C with a strain percentage of .6% using an Advanced Rheometer AR 2000.
  • Figure 49 shows a cross section of the three-dimensional voltage profile calculation for the experimental setup in Figure 30 used to obtain the results seen in Figure 38 (Left).
  • the collector is at the top, the nozzle is at the bottom and only two inter-electrodes are shown, i.e., one grounded (right) and one at 5 kV (left).
  • Figure 50 shows a cross section of the three-dimensional electric field line calculation for the experimental setup used to obtain the results seen in Figure 38 (Left).
  • the collector is at the top, the nozzle is at the bottom and only two inter-electrodes are shown, i.e., one grounded (right) and one at 5 kV (left).
  • Figure 51 shows scaled CAD depiction of the injection chamber (without dielectrics), and the trajectory of the electrospun polymer solution (shown as a spring and dashpot model as discussed above). This CAD model is imported into Comsol 5.3 to analyze the electric field strength between the intermediary electrodes (see Figures 48-49).
  • Figures 52A and 52B depict a system according to another embodiment of the present disclosure, wherein Figure 52B shows a detail view of the system of Figure 52A.
  • Figure 53 is a flowchart showing a method according to another embodiment of the present disclosure.
  • Ranges of values are disclosed herein. The ranges set out a lower limit value and an upper limit value. Unless otherwise stated, the ranges include all values to the magnitude of the smallest value (either lower limit value or upper limit value) and ranges between the values of the stated range.
  • the present disclosure provides electrospinning methods and systems.
  • the present disclosure also provides articles of manufacture, which may be made by a system and/or method of the present disclosure.
  • the present disclosure provides electrospinning systems.
  • the present disclosure may be embodied as an electrospinning system 10 (see, e.g., Figures 52A and 52B).
  • a nozzle 12 is configured to dispense a solidifiable fluid as a fiber stream biased to a first DC voltage.
  • the nozzle 12 may be, for example, a syringe needle.
  • a collector 20 is spaced apart from the nozzle 12.
  • the collector 20 may be a plate or any other suitable shape as will be recognized by a person of skill in the art in light of the present disclosure.
  • the collector 20 is biased to a second DC voltage which is selected to attract the solidifiable fluid biased at the first DC voltage.
  • the collector 20 and nozzle 12 can have various arrangements.
  • the collector plate and needle are vertically arranged.
  • the flow direction may be opposite the direction of gravity (i.e., the collector 20 is arranged vertically above the nozzle 12).
  • the system 10 further includes a plurality of inter-electrodes 30 arranged at a location between the nozzle 12 and the collector 20.
  • the plurality of inter-electrodes 30 may be arranged on a first plane where the first plane is orthogonal to a direct stream path (the path along the shortest distance between the nozzle 12 and the collector 20— identified as 'A' in Figure 52A).
  • the plurality of inter-electrodes 30 may be arranged circumferentially around an direct stream path A.
  • the plurality of inter-electrodes may any number of inter-electrodes 30, for example, any even number of inter-electrodes 32.
  • the system 10 may include two to twelve inter-electrodes 32 or more.
  • Figures 52A and 52B depict a non-limiting embodiment having six inter-electrodes 32 arranged circumferentially around the direct stream path A.
  • the inter-electrodes 32 may be arranged symmetrically or asymmetrically.
  • the electrodes are not directly connected (e.g., disposed) on the collector.
  • the system 10 includes a voltage generator 40 in electrical communication with the plurality of inter-electrodes 30.
  • the voltage generator 40 is configured to apply a voltage to the inter-electrodes 32 (as further described in the sections marked as "Examples" below).
  • the voltage generator 40 may comprise a plurality of voltage generators.
  • the voltage generator 40 comprises a plurality of voltage generators corresponding to the number of inter-electrodes 32, and each inter-electrode 32 may be in electrical communication with a corresponding voltage generator.
  • the voltage generator 40 may comprise a function generator.
  • the system 10 may include a plurality of actuators 34 configured to move the plurality of inter-electrodes 30.
  • Each actuator 36 of the plurality of actuators 34 is configured to move at least one inter-electrode 32.
  • the number of actuators is equal to the number of inter-electrodes.
  • each actuator may be configured to move two inter-electrodes, for example, two opposing inter-electrodes (on opposite sides of the direct stream path.
  • Embodiments of the present disclosure can comprise various actuators and/or combinations of actuators.
  • the actuators are linear driving actuators and/or stepper motors.
  • each actuator is configured to move one or more inter-electrodes closer to or further from the direct stream path A (i.e., radially along the first plane). In this way, the effect on a fiber stream of a voltage potential applied to an inter-electrode may be increased (moving the inter-electrode closer to the direct stream path A) or decreased (moving the inter-electrode away from the direct stream path A).
  • the system 10 includes a stage actuator 22 configured to move the collector.
  • a stage actuator 22 may be configured to rotate the collector 20 about an axis which is parallel to the direct stream path A.
  • the stage actuator may be configured to translate the collector 20 closer to or further from the nozzle 12.
  • Such a stage actuator 22 may be configured to rotate and translate the collector 20.
  • the system 10 may include a nozzle actuator 14 configured to move the nozzle 12.
  • the nozzle actuator 14 may be configured to move the nozzle 12 closer to or further from the collector 20.
  • the systems may be referred to as polymer accelerators.
  • the systems can provide continuous morphologies of aligned nanofibers.
  • the material includes a polymer. Any polymer that can be electrospun can be used. Examples of suitable polymers are known in the art.
  • the material comprises deionized water and polyethylene oxide.
  • the material is an aqueous polymer solution.
  • the polymer solutions of the material involve exotic or encapsulated particles, e.g., conductive, magnetic materials, DNA, etc.
  • first DC voltage is a positive voltage and the collector is 0 VDC or a negative voltage.
  • the first DC voltage may be selected as any value from +2,000 VDC to +20,000 VDC or greater
  • the second DC voltage may be selected from any value from 0 VDC to -20,000 VDC or lower.
  • the first DC voltage is a negative voltage and the second DC voltage is 0 VDC or a positive voltage.
  • the first DC voltage may be selected as any value from -2,000 VDC to -20,000 VDC or lower
  • the second DC voltage may be selected from any value from 0 VDC to +20,000 VDC or greater.
  • the inter-electrodes are biased to a voltage (which may vary) which is generally between the first DC voltage and the second DC voltage.
  • the midstream voltage may be selected such that no material is collected on an inter-electrode.
  • the present disclosure provides electrospinning methods.
  • the methods can be carried out using systems of the present disclosure.
  • a solidifiable fluid is dispensed 103 from a nozzle.
  • the dispensed 103 fluid is biased at a first DC voltage.
  • the method 100 includes drawing 106 a fiber stream from the dispensed 103 fluid along a direct stream path using a collector (as described above, along a path of the shortest distance from the nozzle to the collector).
  • the biased fiber stream is drawn 106 to the collector by biasing the collector to a second DC voltage selected to attract the fluid.
  • the fiber stream may be biased to a voltage of 13,000 volts DC, and the collector may be at -2,600 volts DC (e.g., grounded). In this way, the fiber stream dispensed from the nozzle is attracted to the biased collector.
  • Other suitable voltages may be used as described above and within the examples below.
  • a midstream voltage is applied 109 to at least one electrode of a plurality of inter- electrodes causing the fiber stream to move.
  • the fiber stream may be caused to move in a direction generally orthogonal to the direct stream path.
  • a midstream voltage may be applied 109 such that five inter-electrodes are biased to 5,000 VDC and one inter-electrode is at 0 VDC. In this way, a fiber stream may be moved in a direction towards the grounded inter-electrode and away from the inter-electrodes biased to 5,000 VDC.
  • the plurality of inter-electrodes are arranged in a first plane, wherein the first plane is orthogonal to the direct stream path.
  • the collector is moved 112 relative to the nozzle.
  • the collector may be rotated about an axis parallel to the direct stream path.
  • the collector may be translated in a direction orthogonal to and/or parallel to the direct stream path. The collector may be both rotated and translated.
  • one or more inter-electrodes of the plurality of inter- electrodes may be moved 115 relative to the nozzle and/or the collector.
  • the midstream voltage may be varied 118 over time.
  • the midstream voltage may be such that all but one inter-electrode is biased to a voltage of 5,000 VDC, and a single inter-electrode is held at 0 VDC. Then, the inter-electrode held to 0 VDC is switched to a different one of the inter-electrodes. This may continue, for example, in sequence through each inter-electrode.
  • the midstream voltage may be varied 118 in any other way to collect desirable patterns of the material on the collector.
  • the midstream voltage may be oscillated.
  • the midstream voltages is a oscillating voltage, and the oscillating voltage is set to various amplitudes, phases, frequencies and duty cycles, as applied to each electrode independently or in combinations (groups).
  • a method of electrospinning comprises: biasing a collector plate; dispensing a material (e.g., a material described herein) from a needle positioned apart from the collector plate, wherein the material is depositing on the collector plate after the dispensing; and positioning and/or biasing inter-electrodes disposed along a path between the needle and the collector plate.
  • a material e.g., a material described herein
  • the depositing may be adjusted by tuning at least one parameter selected from the group consisting of a distance between the nozzle and an origin (where the origin is located at the intersection of the inter-electrode plane and the direct stream path), a distance between the collector and the origin, a distance between each of the inter-electrodes and the origin, voltages of the nozzle and/or the collector, peak-to-peak voltages of the inter-electrodes, frequency, duty cycle, and relative phases of each pulse.
  • the methods can be used to form various shapes of electrospun fibers.
  • the fibers can be of different sizes (e.g., diameters).
  • the fibers are nanofibers having at least one nanoscale dimension (e.g., a width/diameter of 100 nm to about 1 micron).
  • a method comprises forming (e.g., drawing) a two-dimensional geometry on the collector with the material.
  • the positioning and/or biasing may include using a continuously phased oscillation to accelerate (e.g., centripetally and/or linearly) ajet of the material with respect to an x-y plane in a sequential manner.
  • Additional non-limiting examples of articles include non-transitory computer readable media storing a program configured to instruct a processor to perform the positioning and/or biasing and the like.
  • the present disclosure provides articles of manufacture.
  • An article may be produced using a system and/or method of the present disclosure.
  • An article may have various shapes. Non-limiting examples of shapes include circle, polygons, and the like. In an example, an article has a non-linear shape. An article may be flexible. In various examples, an article has a two-dimensional geometry. In various examples, an article comprises a plurality of layers forming a three-dimensional shape, where each layer is a particular shape, which may be the same shape or a different shape than one or more of the other layers, formed by a plurality of electrospun fibers (e.g., electrospun nanofibers). The article may be formed of a material comprising an aqueous polymer solution. In some examples, the material comprises a polymer solution involving exotic or encapsulated particles, e.g., conductive, magnetic materials, DNA, etc.
  • the fibers of an article of manufacture or an individual layer or layers of an article of manufacture may be substantially aligned (e.g., aligned).
  • the fibers or a portion thereof of an article of manufacture or an individual layer or layers are conducting (e.g., formed from a conducting polymer).
  • the fibers or a portion thereof of an article of manufacture or an individual layer or layers are not randomly distributed.
  • Non-limiting examples of articles of manufacture include sensors (e.g., biosensors, chemical sensors, electronic sensors, and combinations thereof, and the like), fuel cells or components thereof, tissue scaffolding, optical components (e.g., optical polarizers and the like), electrical components (e.g., conductors, resistors, capacitors, and the like), filtration devices, drug-delivery systems, and component(s) thereof.
  • sensors e.g., biosensors, chemical sensors, electronic sensors, and combinations thereof, and the like
  • fuel cells or components thereof tissue scaffolding
  • optical components e.g., optical polarizers and the like
  • electrical components e.g., conductors, resistors, capacitors, and the like
  • filtration devices e.g., drug-delivery systems, and component(s) thereof.
  • An article of manufacture may be integrated in another article of manufacture.
  • an article of manufacture e.g., a sensor
  • Such articles of manufacture may be referred to as a wearable electronics.
  • a method of electrospinning comprising:
  • Statement 2 A method according to Statement 1, wherein the plurality of inter-electrodes is arranged in a first plane, the first plane being orthogonal to the direct stream path.
  • Statement 3 A method according to any of Statements 1-2, further comprising moving the collector relative to the nozzle.
  • Statement 4 A method according to any of Statements 1-3, wherein the collector is rotated about an axis parallel to the direct stream path.
  • Statement 5 A method according to any of Statements 1-4, wherein the collector is translated in a direction orthogonal to and/or parallel to the direct stream path.
  • Statement 6 A method according to any of Statements 1-5, further comprising moving one or more electrodes of the plurality of electrodes relative to the nozzle and/or the collector.
  • Statement 7 A method according to any of Statements 1-6, wherein the midstream voltage varies over time.
  • Statement 8 A method according to any of Statements 1-7, wherein the midstream voltage is an oscillating voltage, and the oscillating voltage is set to various amplitudes, phases, frequencies, and/or duty cycles, as applied to each inter-electrode or combinations of inter-electrodes.
  • Statement 9 A method according to any of Statements 1-8, where the midstream voltage is configured to accelerate the fiber stream centripetally with respect to the direct stream path.
  • Statement 10 A method according to any of Statements 1-9, wherein the midstream voltage is configured to accelerate the fiber stream radially with respect to the direct stream path.
  • Statement 11 A method according to any of Statements 1-10, wherein the solidifiable fluid comprises a polymer solution.
  • An electrospinning system comprising:
  • a nozzle configured to dispense a solidifiable fluid as a fiber stream biased to a first DC voltage; a collector spaced apart from the nozzle, wherein the collector is biased to a second DC voltage, and the second DC voltage is selected to attract the fiber stream in a flow direction;
  • a plurality of inter-electrodes arranged on a first plane orthogonal to the flow direction, wherein the first plane is located between the nozzle and the collector; and a voltage generator in electrical communication with the plurality of inter-electrodes, wherein the voltage generator is configured to apply a midstream voltage to the inter-electrodes.
  • Statement 14 A system according to Statement 13, further comprising a plurality of actuators configured to move the plurality of inter-electrodes relative to the nozzle and/or the collector.
  • Statement 15 A system according to any of Statements 13-14, wherein the actuators are linear driving mechanisms and/or stepper motors.
  • Statement 16 A system according to any of Statements 13-15, further comprising a stage actuator for rotating the collector about an axis substantially parallel to the direct stream path and/or moving the collector relative to the nozzle.
  • Statement 17 A system according to any of Statements 13-16, further comprising a nozzle actuator for moving the nozzle relative to the collector.
  • Statement 18 A system according to any of Statements 13-17, wherein the voltage generator is configured to apply an oscillating voltage to the plurality of inter-electrodes.
  • Statement 19 A system according to any of Statements 13-18, wherein the oscillating voltage applied to each inter-electrode of the plurality of inter-electrodes is phase-shifted relative to the oscillating voltage applied to one or more other inter-electrodes.
  • Statement 20 A system according to any of Statements 13-19, further comprising a controller in operable communication with the voltage generator, wherein the controller is programmed to instruct the voltage generator to generate the time-dependent voltage.
  • Statement 21 A system according to any of Statements 13-20, further comprising a plurality of actuators in operable communication with the controller, the plurality of actuators configured to move the plurality of inter-electrodes relative to the nozzle and/or the collector.
  • Statement 22 An article produced using the method of one of Statements 1-12 and/or the system of one of Statements 13-21.
  • a method consists essentially of a combination of the steps of the methods disclosed herein. In another embodiment, a method consists of such steps.
  • Path control for an electrospun jet was developed for the fabrication of controlled nanofibrous geometries with aligned morphologies.
  • the designs described herein electrically manipulate the jet and prints multi-dimensional nanofibrous structures and incorporates various methods in linear particle acceleration, ion optics, mechanical motion, AC electronics, DC lensing and real-time electrode actuation, to accelerate a charged polymer solution continuously in the x-y plane, during its trajectory in the z-direction. This is done by continuously oscillating the intermediate electric field over several interchangeable electrodes using a novel electromechanical system.
  • a time varying high voltage signal is employed using custom electronics alongside specific switching protocols, which manipulate the electric field at a specific frequency, amplitude, relative phase difference or a combination thereof to control various deposition patterns.
  • x-y accelerations e.g., linear and/or centripetal x-y
  • stepper-motors (0.9° steps at 400 steps per revolution) drive a rotary-linear actuation mechanism to drive each conductive element within the chamber, i.e., the syringe needle, the collector and each inter-electrode.
  • the metrics of actuation with are achieved with respect to a central origin ( Figure 3). Since high voltage is necessarily applied to each conductive element, a blend of Acetal, Delrin, Teflon and high- density polyethylene (HDPE) is utilized, as they are good electrical insulators and are easily machined. 5/16"-18 threaded rod is also used to achieve displacement accuracies of less than ⁇ . ⁇ '.
  • a remote control as well as an algorithm preprogrammed into a microcontroller is used.
  • a Harvard Apparatus infusion pump rated with an accuracy of ⁇ 0.25%, feeds a
  • the polymer solution used in this experiment is a 10% mixture of deionized water and Polyethylene Oxide (PEO), with a molecular weight of 600, 000 (Sigma Aldrich).
  • Six, high-voltage amplifiers are designed using 6BK4B vacuum triodes in a common-cathode configuration, which are driven by a Spellman SL150 power supply, rated from 0-15 kV at 0-10 mA.
  • the components of the amplifier are chosen with the SL150 current rating in mind.
  • a bypass cathode resistor of 4.4k and a load resistance of 10M are chosen to obtain a Q-point of .39 mA with a grid voltage of 1. 7 V, which can be sufficiently handled with a Tektronix AFG2021 function generator (one for each of the six amplifiers).
  • a BK Precision 9122A DC power supply is used to drive the filament of the vacuum tube (6.3 V requirements at less than 2A) for thermionic emission.
  • substrate deposition is maintained by tuning the following parameters: the distance between the needle and the origin, the distance between the collector and the origin, the distance between each inter- electrode and the origin, needle and collector voltages, inter-electrode pk-pk voltages, frequency, duty cycle, and the relative phases of each pulse.
  • ⁇ ⁇ is the relative phase
  • DN is the duty cycle for a total of N electrodes
  • n corresponds to one of the n function generators, and subsequently to the nth inter- electrode. This sequentially grounds each inter-electrode with respect to ⁇ ⁇ .
  • the duty cycle is defined as:
  • the inter-electrodes will default to the SL150 output. This creates a DC electric lens with six pointed electrodes. From this, a single spot is obtained on the order of mm, which is shown along the z-axis of the collector in Figure 5(A). Furthermore, it is possible to arbitrarily change the x-y coordinates of the collected spot at the substrate by changing the DC voltage on one of the electrodes (acting as an auxiliary electrode) using a sustained pulse. It is also possible to draw a one-dimensional fibrous pathway between two spots. However, it is possible to draw continuous two-dimensional geometries.
  • the SL150 output is set to 5 kV, the syringe needle to 13 kV and the collector to - 7.3 kV. Since the inter-electrodes reach a minimum of 0 V, a negative voltage on the collector is required to keep the jet from depositing directly onto the inter-electrodes (if interception occurs, a dielectric buildup will diminish the electric field at each point).
  • the collector and the syringe needle are positioned from the origin at 1.25" and 2.5", respectively. A 2" diameter gap is obtained between the inter-electrodes, i. e., each electrode at 1" from the origin.
  • r is the displacement from the central axis and /is the frequency at which the pulses are administered. While this will not resolve the drawing-line width, i.e., the spot diameter ( ⁇ 1 mm), it will increase the rate at which it is drawn around the perimeter. To see how this works, one may start by increasing the frequency from 1 Hz to 15 Hz. From Figure 6(B) and Figure 7, the transition from a discrete pattern to a smooth circle can be seen. From this continuous deposition partem, a more continuous morphology can be expected.
  • the syringe needle is set to 13 kV, the collector to -2.6 kV and set the inter-electrodes to oscillate between 0 V and 4.78 kV.
  • the relative phase shift between each pulse will be 11.1 ms.
  • the syringe needle and the collector are both set at 3" from the origin.
  • the inter-electrode lensing diameter is set at 1.5" from the origin.
  • deposition radius of the circle It is also possible to change the deposition radius of the circle. This can be accomplished in two different ways: by changing the relative distances of each electrode or by changing the frequency. To change the radius by electrode displacement, one can use the same voltage on the syringe needle and inter-electrodes, but change the syringe needle and the collector from 3" to 4.5" from the origin. It is then possible to change the collector voltage from -26 kVto -9.2 kV. From this, the deposition radius of the circle will decrease by a factor of two
  • inter-electrodes can be displaced from the origin by .75", and space the collector and needle from the origin by 1.25". From Figure 10, one can see a more aligned fiber from increasing the centripetal acceleration of the jet.
  • the polymer jet may be intercepted midway by one of the grounded electrodes ( Figure 12). This may cause an accumulation of polymer residue on the tip of the inter-electrodes, forming a dielectric build up on its surface.
  • it provides the option to print structured nanofibrous material directly onto the electrodes to be collected separately.
  • the fibers printed here may possess some alignment permutations that aren't typically available using DC voltages. Nevertheless, when attempting to deposit the jet onto the actual collector, such dielectric build up will minimize the electric field in its vicinity so each electrode should be cleaned when necessary.
  • each function generator (8.) The syringe pump (4.) holding the syringe (6.) contains a solution of polymer fibers (and sometimes other mixtures), which are pushed at various volumes per unit time down a tube to the tip of the syringe needle (5.).
  • the tip of the needle is connected to a positive high-voltage power supply (1.) and the collector plate (17.) is connected to a negative power supply (2.) as seen in Figure 14.
  • the copper electrodes, in between the needle and the electrodes are pulsed by the amplifiers (7.) and driven at various duty cycles, frequencies, amplitudes and relative phases to manipulate the electric field along the jet path continuously. This electric field is used to manipulate the charged polymer solution into making the patterns seen in Figure 19.
  • a Tektronix P6015A high-voltage probe (44.) was utilized to measure the voltage at the plate of the triode, (l ⁇ ,), while a high-voltage power supply (2.), V suppiy was varied.
  • a multi-meter was connected at the cathode of the triode (V k ) to measure the bias value, and thus the quiescent operation.
  • FIG 23 shows an exploded view of the driving mechanism used to move the electrodes, collector plate, and syringe needle with respect to each other.
  • the driving mechanism used to move the electrodes, collector plate, and syringe needle with respect to each other.
  • the copper electrodes (11.) To electrically insulate the system/user from the high-voltage being pulsed on the copper electrodes (11.), HDPE, Teflon and Delrin is used.
  • the Teflon spacer As ach copper electrode is threaded into the Teflon spacer (10.), the high-voltage wiring (3.), which is connected to the amplifier (7.), is fed through the slotted cylinder (15.) and connected to the bottom of the electrode.
  • the Teflon spacer is then threaded into the Delrin cylinder, which is inserted into a Delrin sleeve (16.).
  • the threaded rod (14.) is threaded on one end into the Delrin cylinder (15); on the other end, it is fastened to the stepper motor (21.).
  • an oval set screw is inserted (18.) into the side of the Delrin sleeve (16.), which is also fed into the side of the Delrin cylinder (15.).
  • the entire length of the cylinder is then notched for longer linear displacements (15.).
  • This driving mechanism provides a means to translate the rotational momentum of the stepper motors into linear motion. Since the electric field is dependent on the distance of each electrode in the system, this provides a way to change the electric field in real-time using an algorithm or a remote control.
  • the syringe needle and collector operate in the exact same way.
  • a remote control is connected to a microcontroller, which processes the buttons being pressed to drive cylinder displacements.
  • the stepper motors are controlled via pulse width modulation that is also processed by another microcontroller. This allows for real-time control of the electric field without changing the amplitude settings of the amplifier. Moving the electrodes, collector, and syringe needle at various distances, while changing their voltages and other settings, allows for the ability print various geometries.
  • An algorithm programmed into the microcontroller can also be used to automate the process.
  • This invention can be used to print 2D geometries composed of various polymers for applications in tissue engineering, sol-gel precursors, nano-wiring, filtration, energy production/fuel cells, chemical sensors, and drug delivery systems (to name a few).
  • a novel jet deflection protocol was developed for the electrospinning process to generate nanonbrous materials with pre-determined geometries. This is achieved by continuously oscillating the intermediate electric field at various frequencies by supplying a time-varying, high-voltage signal to several intermediate electrodes using a series of custom high-voltage amplifiers alongside various switching protocols. Each time-varying high-voltage signal is pulsed at a specific frequency, duty cycle, amplitude, and relative phase, to create different oscillation sequences for the charged jet to follow. The positively charged polymer jet is then deflected in a predetermined manner to produce different geometries of nanofibrous material.
  • the system is illustrated in Figure 30. It consists of one injection nozzle, a collector electrode, and six intermediate electrodes (inter-electrodes) that are evenly spaced in the horizontal (x-y) plane, intermediary to the injection nozzle and the collector.
  • the number of inter-electrodes and their positions can vary depending on different applications.
  • the flight path of the polymer jet is oriented vertically with the injection point (nozzle) positioned at the base of the system, and the collector above it.
  • Each inter- electrode is connected to an electrically insulated linear driving mechanism so that the distance between the tip of the inter-electrode and the origin (defined in Figure 30), can be individually varied electronically.
  • the nozzle and collector are also connected to a linear electromechanical driving mechanism so as to vary their respective distances from the origin when necessary.
  • a detailed description of the experimental setup can be found in the supplementary information (shown in Figure 44).
  • FIG. 31 The output of a sequentially oscillating, high-voltage source is connected to each inter-electrode to create the necessary electric field needed to manipulate the jet trajectory.
  • Each pulse is generated using a custom high-voltage vacuum tube amplifier, the principle of which is illustrated in Figure 31.
  • Low voltage oscillations from several function generators are connected to the grid of each vacuum tube to suppress the current therein, or short circuit the anode to cathode to produce the desired oscillating high-voltage signal at the plate of each tube.
  • Each pulse is triggered to continuously deflect the jet for two dimensional control over the plane of deposition.
  • Figure 32 shows a low-voltage input oscillation at the grid of the vacuum tube and a corresponding high-voltage output at the plate. These signals correspond with the before-and-after images of the deflected polymer jet shown in Figure 33.
  • substrate deposition by tuning the following parameters: 1) the distance between the needle and the origin, 2) the distance between the collector and the origin, 3) the distance between each inter-electrode and the origin, 4) the needle and collector voltages, 5) the inter-electrode pk-pk voltages, and 6) the amplitude, frequency, duty cycle, as well as the relative phases of each pulse.
  • ⁇ ⁇ is the relative phase in seconds, /is the frequency in Hz
  • D n is the % duty cycle for a total of N electrodes; while n corresponds to one of the six function generators (and subsequently to the nth inter-electrode). This grounds each electrode sequentially with respect to ⁇ ⁇ .
  • the duty cycle is defined as:
  • Polyethylene Oxide (PEO) in deionized (DI) water The molecular weight of the polymer is Mw
  • Table 1 Physical properties of the polymer solution.
  • the relative phase shift between each pulse can be calculated to achieve more continuous geometries.
  • N 6
  • the relative phase shift between each pulse can be calculated to achieve more continuous geometries.
  • This transition can be seen in Figure 37, as we transitioned from a discrete deposition of points to a smooth circle.
  • we set the syringe needle to 13 kV, the collector to -2.6 kV and set the inter-electrodes to oscillate between 0 V and 4.78 kV.
  • the syringe needle and the collector were both set at -76.2 mm and 76.2 mm from the origin, respectively.
  • the inter-electrode lensing radius was set at 19.1 mm from the z-axis.
  • Table 2 Deposition diameters, Doe P , by changing the electrode distances and voltages (with fixed frequencies).
  • Table 3 Deposition diameters, DDep, due to changing the frequency (with fixed electrode distances and voltages).
  • Fiber alignment can also be achieved by cross-deposition using a set of symmetrically opposing electrodes driven 90° out of phase with a square wave pulse between 10 Hz and 45 Hz.
  • the emitted jet is positively charged, it accelerated toward the inter- electrodes and onward to the collector. If the collector is not sufficiently negative, the polymer jet may be intercepted midway by one of the grounded electrodes ( Figure 43). This may cause an accumulation of polymer residue on the tip of the inter-electrodes, forming a dielectric build up on the surface of the conductor. This is not ideal, and may transmit unwanted current between grounded and high voltage inter-electrodes (loading the circuit and potentially damaging the final material) but it could provide the option to print structured nanofibrous material directly onto the electrodes to be collected separately. However, when attempting to deposit the jet onto the actual collector, such dielectric build up will minimize the electric field in its vicinity so it should be cleaned when necessary.
  • a new electrospinning procedure was developed to continuously accelerate a charged polymer jet (linearly and/or centripetally) in two dimensions to print aligned nanofibers with predetermined geometries. This is achieved by oscillating an electric field in the x-y plane during its trajectory in the z-direction using custom high-voltage amplifiers connected to several electrodes placed intermediary along the flight path. Novel switching protocols are utilized to produce sequential low-voltage pulses at the amplifiers, each with various duty cycles, amplitudes, frequencies and relative phases, to deflect the jet in a controlled manner. While this example focuses on the ability to print pre-determined nanofibrous geometries in two dimensions, it demonstrates the potential for further developments in stacking controlled nanofibrous geometries in three dimensions using jet deflection technology.
  • inter-electrodes could be designed in various shapes, e.g., with a much larger ⁇ ratio, where L z is the length of each inter-electrode in the z-direction and D is the diameter between opposing inter-electrodes in the x-y plane
  • point-like geometries are chosen for two reasons: 1) they facilitate in demonstrating the electrospun pathway for point-like deposition (see Figure 35), and 2) they are relatively easy to maintain and clean (see Figure 43).
  • Each inter- electrode is 12.7 mm in length, 3.175 mm in diameter, made of super-conductive-copper 101, and attached to an insulated mechanical driving mechanism.
  • each driver is machined to be oriented 60° from adjacent inter-electrodes in a segmented, but symmetrical, electric lens formation.
  • Eight stepper-motors (0.9° steps at 400 steps per revolution) provide linear actuation to move each conductor in the system, i.e., the nozzle, collector and inter- electrodes, forward or backward with respect to a central origin, which is chosen to be at the center of the inter-electrodes.
  • a Harvard Apparatus infusion pump feeds a blunt 23 gauge, stainless steel needle (nozzle) at a rate of 0.5 mL/hr.
  • a Gamma High Voltage Research, DC power supply rated at 0 - 30 kV, 0 - 200 ⁇ is connected to the syringe needle (with little to no current requirement), and a Spellman SL300, (negative) DC power supply, rated at 0 - (-40 kV), 0 - 7.5 mA, is connected to the collector.
  • High-voltage amplifiers are built using 6BK4B vacuum triodes in a common- cathode configuration, each driven by a Spellman SL150 power supply, rated at 0 - 15 kV from 0 - 10 mA.
  • the components of the amplifier are chosen with the SL150 current rating in mind.
  • the required load lines for a single 6Bk4B amplifier are drawn in Figure 45.
  • the required bypass cathode resistor of 4.4k and a load resistance of 10 M is used to obtain a Q-point of .39 mA with a grid voltage of 1.7 V. This is sufficiently handled with a Tektronix AFG2021 function generator (one for each of the six amplifiers).
  • a BK Precision 9122A (positive) DC power supply is used to drive the filament of the vacuum tube at 6.3 V, requiring less than a total of 2 A for thermionic emission (at quiescent conditions for each tube). From this, we are able to maintain -5 V of -10 V at the grid of each vacuum tube to suppress the current therein to produce high voltage at the plate.
  • the surface tension of the same solution is measured to be 30.95 (m-N)/m at room temperature, i.e., at 21 °C, using a KSV Sigma 701 and a T107 Wilhelmy probe with a cross sectional width of 19.6 mm, a .1 mm thickness, and a wetted length of 39.4 mm.
  • the vessel is 46 mm in diameter with a 40 mL max volume. This method used a light phase (air) wetting depth with an upward and downward velocity of 6 mm and 20 mm/min, respectively.
  • Rheometer AR2000 with a 20 mm, 4°, steel-cone attachment to measure the loss modulus G" and the storage modulus G' for the solution.
  • a frequency sweep from 1 to 10 Hz, with 20 sample points, at 25 °C using a strain percentage of .6% (see Figure 48).
  • FIG 33 we will need to utilize the specific boundary conditions, electrode architecture and relative distances used in our experiment.
  • a scaled three-dimensional CAD depiction of the experimental setup (without dielectrics) is developed in Autodesk Inventor (see Figure 51) and imported into Comsol 5.3.
  • Comsol is a simulation environment incorporating a finite element method (FEM) and boundary element method (BEM) capability, which can easily handle electrostatics.
  • FEM finite element method
  • BEM boundary element method
  • the origin is specified at the center of the inter- electrodes with each inter-electrode spaced 19.1 mm from the z-axis.
  • the nozzle and collector are set at -76.2 mm and 76.2 mm from the origin along the z-axis, respectively.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Nonwoven Fabrics (AREA)

Abstract

L'invention concerne des méthodes et des systèmes d'électrofilage. Dans une méthode d'électrofilage, un fluide solidifiable est distribué à partir d'une buse et polarisé à une première tension continue. Un flux de fibres est aspiré à partir du fluide à l'aide d'un collecteur polarisé à une seconde tension continue. Le flux de fibres peut être déplacé perpendiculairement à un trajet de flux continu à l'aide d'une pluralité d'inter-électrodes polarisées à une ou plusieurs tensions de flux intermédiaire (qui peuvent varier dans le temps). Le flux de fibres est recueilli sur le collecteur.
PCT/US2018/042354 2017-07-14 2018-07-16 Méthodes et systèmes d'électrofilage WO2019014686A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4015678A1 (fr) * 2020-12-17 2022-06-22 Medizinische Universität Wien Dispositif et procédé de fabrication d'une structure fibreuse anisotropique par électrofilage

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Publication number Priority date Publication date Assignee Title
US20040013819A1 (en) * 2000-10-26 2004-01-22 Haoqing Hou Oriented mesotubular and nantotubular non-wovens
US20090091065A1 (en) * 2007-10-09 2009-04-09 Indian Institute Of Technology Kanpur Electrospinning Apparatus For Producing Nanofibers and Process Thereof
US20120107900A1 (en) * 2008-12-19 2012-05-03 Philipps-Universitat Marburg Electrospun Polymer Fibers Comprising Particles of Bacteria-Containing Hydrogels
US8241537B2 (en) * 2004-07-29 2012-08-14 Taiwan Textile Research Institute Method for manufacturing polymeric fibrils
US8308075B2 (en) * 2005-04-19 2012-11-13 Kamterter Products, Llc Systems for the control and use of fluids and particles

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040013819A1 (en) * 2000-10-26 2004-01-22 Haoqing Hou Oriented mesotubular and nantotubular non-wovens
US8241537B2 (en) * 2004-07-29 2012-08-14 Taiwan Textile Research Institute Method for manufacturing polymeric fibrils
US8308075B2 (en) * 2005-04-19 2012-11-13 Kamterter Products, Llc Systems for the control and use of fluids and particles
US20090091065A1 (en) * 2007-10-09 2009-04-09 Indian Institute Of Technology Kanpur Electrospinning Apparatus For Producing Nanofibers and Process Thereof
US20120107900A1 (en) * 2008-12-19 2012-05-03 Philipps-Universitat Marburg Electrospun Polymer Fibers Comprising Particles of Bacteria-Containing Hydrogels

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4015678A1 (fr) * 2020-12-17 2022-06-22 Medizinische Universität Wien Dispositif et procédé de fabrication d'une structure fibreuse anisotropique par électrofilage
WO2022129326A1 (fr) * 2020-12-17 2022-06-23 Medizinische Universität Wien Dispositif et procédé de fabrication d'une structure fibreuse anisotrope par électrofilage

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