EP2045375B1 - Vorrichtung und Verfahren für Elektrospinning von 2D- oder 3D-Strukturen von Mikro- bzw. Nanofasermaterialien - Google Patents

Vorrichtung und Verfahren für Elektrospinning von 2D- oder 3D-Strukturen von Mikro- bzw. Nanofasermaterialien Download PDF

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Publication number
EP2045375B1
EP2045375B1 EP07117780A EP07117780A EP2045375B1 EP 2045375 B1 EP2045375 B1 EP 2045375B1 EP 07117780 A EP07117780 A EP 07117780A EP 07117780 A EP07117780 A EP 07117780A EP 2045375 B1 EP2045375 B1 EP 2045375B1
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EP
European Patent Office
Prior art keywords
nano
fibers
micro
electrospinning
electrodes
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EP07117780A
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English (en)
French (fr)
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EP2045375A1 (de
Inventor
Yousef Mohammadi
Akbar Gazme
Masoud Soleimani
Vahid Polymer Engineering Department Haddadi-Asl
Moslemkhani Mohsen
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Stem Cell Technology Co
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Stem Cell Technology Co
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Priority to EP07117780A priority Critical patent/EP2045375B1/de
Priority to DE602007013237T priority patent/DE602007013237D1/de
Priority to AT07117780T priority patent/ATE502140T1/de
Publication of EP2045375A1 publication Critical patent/EP2045375A1/de
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    • 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
    • D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
    • 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
    • D01D7/00—Collecting the newly-spun products

Definitions

  • the present invention relates in general to electrospinning of fiber forming materials, in particular polymer materials, and relates in particular to an apparatus and method for electrospinning 2D- or 3D-structures of micro- or nano-fibrous materials
  • Electrospinning, or electrostatic field-assisted fiber deposition, has been extensively explored as a quick and facile technique for preparing ultrathin fibers with diameters ranging from tens of nanometers to micrometers [ D. Li and Y. N. Xia, Adv. Mater., 16, 1151-70, 2004 and Y. Dzenis, Science, 304, 1917-9, 2004 ]. It is based on electrostatic surface charging of a melt or solution droplet, drawing a jet moving at a high speed toward a grounded stationary or rotating surface. The highly extensional flow results in ultrahigh draw ratios, which lead to the formation of a continuous nanofiber.
  • nanofibers obtained so far are in non-woven form, which are suggested for applications in energy storage, healthcare, biotechnology, environmental engineering, and defense and security [ S. Ramakrishna, K. Fujihara, W. E. Teo, T. Yong, Z. Ma and R. Ramaseshan, Materialstoday, 9(3), 40-50, 2006 ].
  • the drum that is used to collect the nanofibers is rotated at a very high speed up to thousands of revolutions per minute (rpm). Although there is obvious alignment of the nanofibers, the degree of alignment is not very good as there are still a substantial number of misaligned nanofibers collected.
  • the introduction of a sharp pin with a negative potential applied in the rotating drum can be used to create an electric field that leads from the tip of the needle and converges at the sharp pin in the rotating drum [ B. Sundaray, V. Subramanian, T. S. Natarajan, R. Z. Xiang, C. C. Chang and W. S. Fann, Appl. Phys. Lett., 84(7), 1222-1224, 2004 ].
  • the pin in the drum is mounted vertically and it lies directly below the positively charged needle.
  • the distance between the two electrodes is highly limited to maintain the electric field from the needle to the sharp pin.
  • this method of collection may not be suitable when a less volatile solvent which is used to dissolve the polymer.
  • Katta et. al. used a rotating wire drum to collect aligned electrospun nanofibers [ P. Katta, M. Alessandro, R. D. Ramsier and G. G. Chase, Nano. Lett., 4, 2215-2218, 2004 ].
  • the rotation speed of the drum has been reported to be 1 revolution per minute (rpm). This is a much slower rotating speed compared to other nanofiber alignment methods using rotating drum.
  • rpm revolution per minute
  • the aligning of the nanofibers may not be due to the mechanical winding of the nanofibers around its circumference.
  • the electric field profile created by the parallel wires with gaps between them may play a part in aligning the nanofibers.
  • Zussman and co-workers have modified the design of a drum and used a tapered, wheel-like disk as the collector [ A. Theron, E. Zussman and A. L. Yarin, Nanoteclnology, 12, 384-390, 2001 ]. It was found that most of the nanofibers could be collected on the sharp edge. The collected fibers were oriented parallel to each other along the edge. These authors have also simulated the electrostatic field of this configuration and revealed that the field strength increased dramatically near the edge of the disk. Because of the strong electrostatic attraction, the charged nanofibers were continuously wound on the edge when the disk was rotating at a relatively high speed. They further demonstrated that nanofiber crossbars could be readily fabricated using this collector.
  • US 4,689,186 discloses a method to fabricate tubular products for blood vessel prosthesis and urinary and bile duct applications.
  • deposited fibers can be circumferentially oriented substantially by employing an auxiliary electrical field.
  • the auxiliary electrode made of parallel conducting strips was given a negative voltage such that the electric field extends from the positively charged needle to the auxiliary electrodes.
  • the parallel conducting strips has the effect of concentrating the electric field along the orientation of the parallel strips.
  • the electrospinning jet has a greater tendency to spin in the direction of the orientation of the strips.
  • aligned nanofibers along the circumference of the nanofibers can be obtained at a lower rotation speed as compared to using a rotating mandrel alone.
  • parallel knife-edged bars can be used instead of strips [ W. E. Teo, M. Kotaki, X. M. Mo and S. Ramakrishna, Nanotechnology, 16, 918-924, 2005 ].
  • Xia and Li demonstrated that the geometrical configuration of a conductive collector had a profound effect on the orientation of electrospun nanofibers [ D. Li, Y. Wang and Y. Xia, Nano Lett., 3(8), 1167-1171, 2003 ].
  • electrospun nanofibers could be uniaxially aligned over long length scales during the spinning process.
  • Xia and Li disclose that it is convenient to transfer the aligned nanofibers onto other solid substrates for further processing steps and applications.
  • modification to the setup can be used to achieve more complicated arrangement of the electrospun nanofibers.
  • repulsion caused by the charges on the deposited nanofibers means that the collection time cannot be more than a few minutes thus this method may not be suitable for collection of a large patterned mesh or thick patterned mesh.
  • US 6,713,011 B2 discloses an apparatus and a method for electrospinning polymer fibers and membranes according to the preamble of claim 1.
  • the apparatus comprises an array of electrospinning spinnerets electrically charged at a first potential.
  • a ground plate is positioned below the array such that an electric field is created between the charged spinnerets and the ground plate, which causes tiny jets of a conducting, fiber-forming fluid to be ejected from the spinnerets and spray towards the ground plate, forming sub-micron diameter filaments or fibers.
  • a moving support membrane is positioned between the charged spinnerets and the ground plate to collect the fibers and to form an interconnected web of the fibers.
  • the support membrane is substantially flat and moves passed the spinnerets by being unwinded from an upstream unwind roll and winded onto a downstream rewind roll.
  • a closely-related object of the present invention is to control the density and other physical, morphological, mechanical, biological, and chemical properties of the micro- or nano-fibrous materials, produced through the electrospinning process. It is a further closely-related object of the present invention, to enable a reliable design and production of 2D and/or 3D structures composed of aligned micro- or nano-fibers of the same or different materials.
  • an apparatus for electrospinning 2D- or 3D-structures of micro- or nano-fibrous materials in particular for electrospinning 2D- or 3D-structures consisting of or comprising a plurality of precisely aligned and densely packed micro- or nano-fibrous materials, comprising at least one electrospinning spinneret being electrically charged at a first potential; electrode means disposed adjacent said at least one electrospinning spinneret and being electrically charged at a second potential different from said first potential to thereby generate an electric field between said at least one electro spinning spinneret and said associated electrode means for aligning micro- or nano-fibers injected by said at least one electrospinning spinneret; and collecting means for collecting micro- or nano-fibers injected by a respective spinneret and aligned by said associated electrode means.
  • the electrode means comprises at least two conductive electrodes, which are disposed in parallel with each other and rotate in the same rotating direction, wherein the collecting means is movably disposed between said at least two conductive electrodes for collecting said aligned micro- or nano-fibers.
  • the two electrodes which are disposed spaced apart from each other and in parallel with each other serve to generate an electric field of a precisely specifiable strength and electric field distribution that is virtually not effected by external stray fields and other sources.
  • a droplet of a fiber-forming material, in particular melt or solution is ejected by the associated spinneret(s) into the space between the electrodes to thereby form stretched micro- or nano-fibers that are immediately aligned with each other in a precise positional relationship with respect to each other due to the electric field generated by the electrodes.
  • the two opposite ends of these fibers adhere to the circumference or surface of the electrodes due to electrostatic and/or adhesive forces.
  • the fibers After being aligned the fibers are transported away from the location of injection to a collecting means disposed downstream in the rotating direction of the rotating electrodes. Thus, further droplets can be injected substantially unhindered and unaffected by any previously generated fibers to thereby form fresh micro- or nano-fibers.
  • a substantially continuous or batch-wise feed of precisely aligned micro- or nano-fibers can be generated that adhere to the circumference or surface of the rotating electrodes. This feed of precisely micro- or nano-fibers is continuously transported to the downstream collecting means to be deposited onto the surface thereof.
  • the alignment and further parameters of the feed such as density, thickness and further properties of the fibers can be precisely controlled, which enables the production of hybrid materials consisting of or comprising a plurality of micro- or nano-fibers that are arranged in a unique densely packed arrangement in precise alignment with each other and precisely controllable geometrical configuration.
  • hybrid materials consisting of or comprising a plurality of micro- or nano-fibers that are arranged in a unique densely packed arrangement in precise alignment with each other and precisely controllable geometrical configuration.
  • the electrodes can have a virtually arbitrary geometric configuration, e.g. can comprise curved or bulged surfaces that are disposed in parallel with each other. More preferably the surfaces of the electrodes are flat enabling the generation of a predetermined electric field according to the well-known parallel-plate-capacitor-principle. Even more preferably the circumference of the electrodes is circumventing, in particular elliptical or circular shaped. Adherence of the micro- or nano-fibers at the outer circumference of circular disc-shaped electrodes enables a steady and precisely controllable feed of fibers to the downstream collecting means.
  • the oppositely disposed electrodes are rotating synchronously with each other about a common rotating axis, which preferably extends perpendicular to a surface of the electrodes and through a center thereof.
  • the collecting means comprises at least one flat conductive plate or at least one cylindrical mandrel extending perpendicular to a surface of said associated electrodes.
  • the plate or mandrel may bridge substantially the entire gap between the oppositely disposed electrodes although according to other embodiments there may exist a certain gap between the periphery of the plate or mandrel and the surface of the electrodes.
  • the fibers transported with a given velocity towards the surface of the collecting means by the rotating electrodes finally impinge onto the surface of the collecting means and are smoothly peeled off the surface of the electrodes to be deposited on the surface of the collecting means.
  • the orientation and alignment of the fibers remains substantially unchanged as the deposition of the fibers is not affected by the generation of new fibers at the upstream injecting location due to the geometrical separation between the respective spinneret and the associated collecting means.
  • deposition of the fibers on the surface of the collecting means is even less effected if the collecting means is grounded or precisely controlled to a predetermined electrostatic potential, which most preferably is identical to that of the associated electrodes between which the collecting means is disposed.
  • the collecting means can be moved with an e.g. constant or variable linear speed between said associated electrodes and/or can be rotated at an e.g. constant or variable rotating speed about a given or variable rotation axis in the three-dimensional space between said associated electrodes.
  • the conditions during deposition of the aligned fibers, which are transported towards the surface of the collecting means by the rotating electrodes can be varied easily and in a reliable manner, by controlling the speed and orientation of the rotation axis of the collecting means.
  • This enables to vary many different characteristics of the hybrid material deposited on the surface of the collecting means, such as density of the fibers, morphology, homogeneity of the alignment and density of the hybrid material, porosity etc.
  • a relative speed between the associated electrodes and the collecting means can be varied for varying the density of micro- or nano-fibers collected by said collecting means.
  • the relative speed may be varied gradually, stepwise, ramp-like manner or in any other manner, as will become apparent to a person skilled in the art.
  • each of said electrospinning spinnerets is configured for ejecting different materials simultaneously or subsequently or in accordance with any desired time-sequence, in order to enable the deposition of a predetermined mixture of precisely aligned micro- or nano-fibers on the surface of the collecting means, said mixture being determined by the time sequence of actuating the electrospinning spinnerets.
  • the apparatus comprises a plurality of electrospinning spinnerets disposed at different angular positions with respect to a rotating direction of said conductive electrodes. These angular position can be fixed or may be varied continuously, step-wise or in accordance with any desired motion-sequence in order to even further vary the properties, composition and geometrical configuration of the hybrid material deposited onto the surface of the collecting means.
  • a further related aspect of the present invention is directed to a method for electrospinning, in correspondence with the afore-mentioned apparatus.
  • the fiber-forming material ejected by the respective spinneret(s) for generating the micro- or nano-fibers may consist of dissolved and/or molten polymers, ceramics, metals and mixtures of at least two of the afore-mentioned materials and/or different precursors or mixtures thereof.
  • the molten mixtures and/or solutions may contain nanoparticles.
  • nanoparticles are nanoparticles of metals, metal oxides and/or ceramics.
  • Figure 1 shows an apparatus for electrospinning according to a first embodiment of the present invention, capable of precisely controlling both the degree and pattern of the alignment of the micro- or nano-fibers.
  • the apparatus has overall a structure comparable to that of conventional systems and comprises a spinneret for ejecting droplets of fiber-forming material, which is fed by a pump 1 to deliver the electrospinning melt or solution 1.
  • the output of a high-voltage power supply 10, more specifically an AC power supply is applied to the spinneret 3 in order to generate a predetermined potential difference between the spinneret 3 and the grounded electrodes 4A, 4B, for alignment of the produced micro- or nano-fibers 5 (only schematically shown).
  • the micro- or nano-fibers 5 are aligned between the two parallel disc-shaped rotating electrodes 4A and 4B of a conductive material.
  • the disc-shaped electrodes 4A, 4B are grounded via the rotating shaft 7 of electrically conductive material.
  • the electrospun fibers 5 are aligned in parallel with each other between the two rotating electrodes 4A and 4B.
  • the fibers 5 accumulate substantially at the periphery of the disc-shaped electrodes 4A, 4B. These are driven by the motor 6 and via the rotating shaft 7 at a constant angular speed, which of course can also be varied as wished according to further embodiments of the present invention.
  • the two parallel electrodes 4A, 4B are rotated synchronously with each other so that the aligned fibers 5 between the electrodes 4A, 4B are not stretched while being transported by the rotating electrodes.
  • a collector 9 in the form of a flat conductive plate is disposed symmetrically between the two electrodes 4A, 4B.
  • the collector 9 extends substantially perpendicular to the surfaces of the electrodes 4A, 4B and is disposed at a radius smaller than the radius D/2 of the two electrodes 4A, 4B.
  • the collector plate 9 is grounded, although according to further embodiments the collector plate 9 may also be charged to a predetermined electrostatic potential relative to the spinneret 3 and electrodes 4A, 4B, as desired.
  • the fibers 8 experience no electrostatic counter-forces when being deposited on the collector plate so that their alignment remains substantially unaffected white being deposited.
  • the width of the collector plate 9 in x-direction is substantially identical to the distance between the electrodes 4A, 4B, although according to further embodiments this condition may not necessarily be satisfied.
  • the collector plate 9 is coupled with a drive 11 to be moved in radial outward direction of the electrodes and/or rotated between the electrodes 4A, 4B. If one assumes as an example that the collector plate 9 is moved at constant speed in radial outward direction, the fibers 8 will be deposited on the surface of the collector plate 9 in parallel with each other and at a constant density, which is given inter alia by the amount of fibers 5 collected and transported by the rotating electrodes 4A, 4B and the moving speed of the collecting plate 9.
  • the alignment, density and other physical, morphological, mechanical, biological, and chemical properties of the micro- or nano-fibrous materials, produced through the electrospinning process can be controlled precisely and in a reliable manner.
  • FIG. 2 shows a schematic diagram of the different parts of the collector of the present invention.
  • Fig. 2c shows the electric field lines between the two parallel disc-shaped electrodes 4A, 4B.
  • the electric field lines between the two parallel disc-shaped rotating electrodes 4A, 4B are divided into two parts, in a way that the direction of these field lines is toward the circumference of the discs 4A, 4B.
  • the direction of the electrospinning jet between the spinneret 3 and target (collector) is highly dependent on the electric field lines.
  • the electrospinning melt or solution or in other words the micro- or nano-fibers to be produced are alternatively aligned in parallel to one another between the two parallel disc-shaped rotating electrodes 4A, 4B.
  • the aligned fibers are shown as to extend in parallel with each other between the rotating electrodes 4A, 4B to thereby substantially follow the electric field lines. From the location of injection into the space between the electrodes 4A, 4B the fibers are then transported towards the collector plate 9, due to the rotary movement of the disc-shaped electrodes 4A, 4B.
  • the fibers are then moved into immediate vicinity of the collector plate, from where they finally hit the collector plate to be separated from the electrodes 4A, 4B and be deposited onto the surface of the collector plate 9. If the collector plate 9 is not moved the fibers will accumulate on the same location in the form of a stripe-shaped staple of parallel micro- or nano-fibers. In order to avoid an excessive accumulation of fibers on the same location on the collector plate and to efficiently control parameters, such as density and thickness of the layer of micro- or nano-fibers to be deposited onto the collector plate, the collector plate 9 is moved radially outward or outward, as indicated by the double-arrow V in Fig. 2a .
  • a quasi homogeneous layer consisting of micro- or nano-fibers and having a predetermined density is deposited onto the surface of the collector plate, the thickness being determined by parameters of the apparatus itself, such as rotating speed of the electrodes 4A, 4B, the ejection rate of the spinneret 3 and the velocity of the collector plate 9, as will become apparent to a person skilled in the art when studying this description.
  • the properties of the layer to be deposited on the surface of the collector plate 9 can be controlled efficiently and precisely.
  • the space between the two disc-shaped rotating electrodes 4A, 4B is virtually divided into two half space I and II.
  • Half space I is a segment of the space between the two disc-shaped rotating electrodes that is between point N and the collector 9, where the micro- or nano-fibers are most loaded over the collector
  • region II is the remaining half space between the two parallel disc-shaped electrodes 4A, 4B, where literally no micro- or nano-fibers are deposited on the collector 9.
  • the collector 9 can be positioned in the space between the two parallel disc-shaped rotating electrodes 4A, 4B at any point, as desired and/or can be moved with a suitable speed.
  • the collector 9 enters the space between the two parallel disc-shaped rotating electrodes 4A, 4B at a proper speed and point, to thereby adjust the density of the layer of fibers deposited on the collector 9. According to a most preferred embodiment of the present invention, it is preferred that the collector 9 enters the space between the two parallel disc-shaped rotating electrodes 4A, 4B at an appropriate distance from point N.
  • the collector 9 can be driven by the motor 11 to be moved precisely between the two parallel disc-shaped rotating electrodes 4A, 4B at any direction, preferably in a direction perpendicular to the circumference of the disc-shaped rotating electrodes 4A, 4B. This allows preventing the build-up of the micro- or nano-fibers in one section of the collector 9 and also can be used for depositing different number of layers over one another.
  • the collector can be moved stepwise at one or several movements in a direction perpendicular to the circumference of the disc-shaped electrodes 4A, 4B, which can help create more layers in one or several segments of the layer on the collector 9 while keeping the other segments in the vicinity as single layers or layers of different numbers.
  • the collector 9 can also be designed to whirl completely or to some extent with respect to the two parallel disc-shaped rotating electrodes 4A, 4B.
  • the movement of the collector 9 in any of the mentioned directions and with any desired speed(s) can lead to the formation of two or three-dimensional structures of micro- or nano-fibers each layer of which can have same or different materials and/or alignments.
  • the angular speed of the two parallel disc-shaped rotating electrodes 4A, 4B can vary from a minimum value (( ⁇ min >0) up to any desired maximum value.
  • the distance between the two parallel disc-shaped rotating electrodes being a determining factor affecting the length of the aligned micro/nano-fibrous structure, can be designed to be fixed or to vary from a minimum optimum distance H min to a maximum optimum one H max.
  • the distances H min and H max can vary further depending on the materials used for electrospinning.
  • the two parallel disc-shaped rotating electrodes used in the present invention can be of any size and dimensions and they can be either disc-shaped, straps, and/or hallow rings.
  • the discs may also be of the same or of different sizes. It is noteworthy that the smaller is the size of the two parallel disc-shaped rotating electrodes, the harder it is to handle the process. According to a preferred embodiment of the present invention, the diameter of the two parallel disc-shaped rotating electrodes is preferred to be the same and their thickness can be arbitrary.
  • different number of parallel disc-shaped electrodes as well as collectors can be used to build an electrospinning device according to the present invention, however at least two parallel disc-shaped rotating electrodes and one collector are necessary.
  • the number of electrospinning jets and collectors, according to another embodiment of the present invention can vary. However, at least one electrospinning jet and one collector are used.
  • the shape of the collector can be chosen based on the aim of the design of system. However, according to the preferred embodiment of the present invention it is preferred to be round, square, or rectangular. According to the most preferred embodiment of the present invention the shape of the collector is preferred to be rectangular or square.
  • the material used for building the collector can be any proper material of different chemical and/or physical properties. It is also noteworthy that it is preferred that the collector be made of conducting materials. This is due to the fact that, in the case of the application of an insulating material in the construction of the collector, the static charges that have been built on the body of the micro/nano-fibers cannot be discharged to the collector. The layers that have been built first will repel the new micro- or nano-fibers that are being deposited on the 2D/3D produced array of micro- or nano-fibers. Conductive materials lack this disadvantage as a result of their ability to discharge the deposited micro- or nano-fibers.
  • the collector used in the system of the present invention be made of a conductive material, according to another embodiment of the present invention, such aluminum, steel, copper, gold, silver, platinum. According to the most preferred embodiment of the present invention, it is preferred that the collector used in the system be made of aluminum.
  • the collector that is made of a conductive material is connected to the earth or a pole of opposite charge to help the discharge happen with a higher efficiency.
  • the speed of the movement of the collector between the two parallel disc-shaped rotating electrodes, V(t), is another important factor that affects the efficiency of the present method.
  • the radial movement (i.e., movement perpendicular to the circumference of the rotating discs) of the collector in the space between the two parallel disc-shaped rotating electrodes helps avoid the build-up of the produced micro- or nano-fibers in one point of the collector, and rather distribute them evenly all over its surface. It is ineluctable to mention that the higher this speed is the higher the space between the deposited micro- or nano-fibers will be and on the contrary the slower it moves the more dense will become the produced micro- or nano-fibrous structure.
  • the speed of the movement of the collector between the two parallel disc-shaped rotating electrodes can be designed to vary according to any functions of desire or be completely constant over the whole path.
  • the overall (i.e. over the whole layer(s) on the collector) or local (i.e. over one spot of each layer over the collector) density of the aligned micro- or nano-fibers can be determined by determining the speed of the movement of the collector.
  • even the number of the layers in one location of the layer over the collector can also be determined by either stopping the collector at desired intervals or moving it in a perpendicular path in addition to the radial one, or even returning it over a short path in the middle of the overall path of the collector for one to several times.
  • the speed of the movement of the collector is kept constant.
  • the density of the distribution of the micro/nano-fibers can be increased by means of decreasing the constant speed of the movement of the collector, while the density can be decreased by increasing this speed.
  • the minimum and maximum speeds of the movement of the collector are between zero and any positive desired maximum value.
  • Fig. 3a and 3b show an apparatus for the production of different patterns of totally aligned micro/nano-fibers according to another embodiment of the present invention together with the structure of a layered material produced in this manner.
  • the apparatus comprises a plurality of n separate electrospinning spinnerets 3 that are referred to with indices 1 to n. All or some of the jets produced by the spinnerets 3_1 to 3_n can be used to inject the same material or different ones in order to produce different hybrid patterns, e.g. patterns containing different micro/nano-fibrous materials of desire.
  • the spinnerets 3_1 to 3_n are disposed at different angular positions along the circumference of the rotating disc-shaped electrodes 4A and 4B (not shown), spaced apart to each other. These angular positions can either be fixed over the time or can be shifted, e.g. by angular movement of each or individual ones of the spinnerets 3_1 to 3_n. In the later case a driving motor would be associated to each, several or all of the spinnerets 3_1 to 3_n.
  • the spinnerets 3_1 to 3_n can be actuated all at the same time or individually in arbitrary actuation patterns, as desired. Further, the spinnerets 3_1 to 3_n can be used to inject the same or different melts or solutions in order to obtain such hybrid patterns, i.e. patterns containing different micro/nano-fibrous materials, of desire.
  • the width W i of the i-th layered section (with i ranging from 1 to n) of the micro- or nano-fibrous material deposited on the collector 9 and/or the density of each of these sections, composed of different or the same micro/nano-fibrous materials, can be varied by adjusting the constant or variable speed(s) of the collector 9, the speed of the jets, and other effective parameters, irrespective of whether they are superimposed on another layer of another or the same micro/nano-fibrous material or as a single layer
  • the position, angle, and injection rate of the jets and also the position, angle, and speed of the collector can be adjusted so that more than one jet can perform its role over one point of the collector at the same time with the other jet(s).
  • the collector 9 can be rotated horizontally with respect to an axis perpendicular to the surface of the collector 9, i.e. about an axis that is perpendicular to the axis of rotation of the rotating disc-shaped electrodes 4A and 4B.
  • the collector plate 9 By moving the collector plate 9 radially inward (as shown) and/or radially outward with a constant speed v during deposition individual layers will be deposited onto the surface of the collector plate, each layer consisting of a fibers aligned in parallel with each other and with a given unique rotational orientation with respect to the side edges of the collector plate 9.
  • the different aligned micro/nano-fibrous layers are desired to be composed of different materials (hybrid structures)
  • either one jet injecting different materials at desired time intervals
  • a plurality of jets each injecting any desired materials
  • Fig. 6a and Fig. 6b can be designed in the structure of the electrospinning system of the present invention.
  • the collector can have any shapes, sizes, and can be either smooth or with any desired pattern or surface.
  • the collector should have dimensions that let it fit between the two parallel disc-shaped rotating electrodes, and rotate freely in any desired directions.
  • the collector can have other 3D spherical, cubic, or cylindrical structures.
  • the collector is formed as a cylindrical mandrel 9 that extends in a direction in parallel with the axis of rotation of the disc-shaped rotating electrodes 4A, 4B and can be rotated about this axis with the same or a different rotational speed as the rotating electrodes 4A, 4B, as indicated by the index ⁇ '.
  • Such a cylindrical collector 9 can have any length and any diameter provided it does not prevent the formation of the aligned micro/nano-fibers. Furthermore, the cylindrical collector can rotate at any desired speed.
  • dissolved and/or molten polymers, ceramics, metals, and mixtures of one or some of these materials and also different precursors or mixtures thereof capable of forming micro- or nano-fibers by electrospinning can be used in the system according to the present invention.
  • the spinnerets for producing the jets of such materials can be arranged in any desired geometrical alignment.
  • such molten mixtures and/or solutions that additionally contain nanoparticles can be converted to highly aligned micro/nano-fibers of desired patterns using the system of the present invention.
  • such molten mixtures and/or solutions can contain nanoparticles of metals, metal oxides, ceramics, and polymers to be converted to highly aligned micro/nano-fibers of desired patterns using the system of the present invention.
  • 2D and/or 3D matrices composed of highly aligned carbon micro/nano-fibers can be prepared using appropriate precursors and applying the system of the present invention.
  • micro/nano-fibers of different morphologies including porous, flatted or ribbon-like, core-sheath, helical and/or hollow micro/nano-fibers that have already been produced can also be produced using the system of the present invention.
  • microfiber or microfibers' as used herein relates to fibers with strands less than one denier.
  • 'nanofiber or nanofibers' as used herein relates to fibers with diameters less than 100 nanometers. Special properties of micro- or nanofibers make them suitable for a wide range of applications like medical, consumer products, industrial, high-tech applications for aerospace, capacitors, transistors, drug delivery systems, battery separators, energy storage, fuel cells, information technology, and filtration and it is expressly noted that the present application is to cover any of the afore-mentioned applications as well as any related application.

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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)
  • Artificial Filaments (AREA)

Claims (17)

  1. Vorrichtung zum Elektrospinnen von zwei 2D- oder 3D-Strukturen aus Mikro-oder Nanofasermaterialien, umfassend:
    zumindest eine Elektrospinndüse (3), die auf ein erstes Potential elektrisch aufgeladen ist;
    Elektrodenmittel (4A, 4B), die in der Nähe der zumindest einen Elektrospinndüse (3) angeordnet sind und auf ein zweites Potential elektrisch aufgeladen sind, das verschieden zu dem ersten Potential ist, um so ein elektrisches Feld zwischen der zumindest einen Elektrospinndüse (3) und dem zugeordneten Elektrodenmittel zu erzeugen, um Mikro- oder Nanofasern auszurichten, die mit Hilfe der zumindest einen Elektrospinndüse (3) eingespritzt werden; und
    ein Sammelmittel (9), um die Mikro- oder Nanofasern, die mit Hilfe einer jeweiligen Spinndüse eingespritzt werden und mit Hilfe des zugeordneten Elektrodenmittels ausgerichtet werden, einzusammeln bzw. einzufangen;
    dadurch gekennzeichnet, dass das Elektrodenmittel zumindest zwei leitende Elektroden (4A, 4B) umfasst, die parallel zueinander angeordnet sind und sich in der selben Drehrichtung drehen, und
    das Sammelmittel (9) beweglich zwischen den zumindest zwei leitenden Elektroden (4A, 4B) angeordnet ist, um die ausgerichteten Mikro- oder Nanofasern einzusammeln.
  2. Vorrichtung nach Anspruch 1, wobei die Elektroden flache kreisförmige Scheiben sind, die sich synchron zueinander um eine Drehachse drehen.
  3. Vorrichtung nach einem der vorhergehenden Ansprüche, wobei das Sammelmittel zumindest eine flache leitende Scheibe (9) oder zumindest einen zylindrischen Ziehdorn umfasst, der sich senkrecht zu einer Oberfläche der zugeordneten Elektroden erstreckt.
  4. Vorrichtung nach einem der vorhergehenden Ansprüche, wobei das Sammelmittel (9) ausgelegt ist, um sich mit einer konstanten oder variablen Lineargeschwindigkeit zwischen den zugeordneten Elektroden (4A, 4B) zu bewegen und/oder um sich mit einer konstanten oder variablen Geschwindigkeit um eine vorgegebene oder variable Drehachse im dreidimensionalen Raum zwischen den zugeordneten Elektroden zu drehen.
  5. Vorrichtung nach einem der vorhergehenden Ansprüche, wobei eine Relativgeschwindigkeit zwischen den zugeordneten Elektroden und dem Sammelmittel variiert werden kann, um die Dichte der von dem Sammelmittel eingesammelten bzw. eingefangenen Mikro- oder Nanofasern zu variieren.
  6. Vorrichtung nach einem der vorhergehenden Ansprüche, wobei jede der Elektrospinndüsen ausgelegt ist, um unterschiedliche Materialien gleichzeitig oder nacheinander einzuspritzen.
  7. Vorrichtung nach einem der vorhergehenden Ansprüche, wobei die Vorrichtung eine Mehrzahl von Elektrospinndüsen umfasst, die an verschiedenen Winkelstellungen in Bezug zu einer Drehachse der leitenden Elektroden angeordnet sind.
  8. Verfahren zum Elektrospinnen von 2D- oder 3D-Strukturen aus Mikro- oder Nanofasermaterialien mit den Schritten:
    zumindest ein Strahl aus einer Flüssigkeit aus einem faserbildenden Material wird über zumindest eine Elektrospinndüse (3) eingespritzt, die elektrisch auf ein erstes Potential aufgeladen ist;
    ein jeweiliger Strahl wird mit Hilfe eines elektrischen Feldes ausgerichtet, das zwischen Elektrodenmitteln (4A, 4B) erzeugt wird, die in der Nähe der zumindest einen Elektrospinndüse (3) angeordnet sind und elektrisch auf ein zweites Potential aufgeladen sind, das verschieden zu dem ersten Potential ist; und
    ein jeweils ausgerichteter Strahl wird auf einem Sammelmittel (9) eingesammelt bzw. aufgefangen, um die 2D- oder 3D-Strukturen auszubilden, wobei: das elektrische Feld von zumindest zwei leitenden Elektroden (4A, 4B) erzeugt wird, die parallel zueinander angeordnet sind und sich in derselben Drehrichtung drehen, und
    das Sammelmittel (9) zwischen den zumindest zwei Elektroden (4A, 4B) bewegt wird, während dieses die ausgerichteten Mikro- oder Nanofasern sammelt bzw. auffängt.
  9. Verfahren nach Anspruch 8, wobei das elektrische Feld von zumindest zwei flachen kreisförmigen Scheiben erzeugt wird, die sich synchron zueinander um eine Drehachse drehen.
  10. Verfahren nach Anspruch 8 oder 9, wobei die Mikro- oder Nanofasern von zumindest einer flachen leitenden Scheibe (9) oder von zumindest einem zylinderförmigen Ziehdorn eingesammelt bzw. aufgefangen werden, der sich senkrecht zu einer Oberfläche der zugeordneten Elektroden erstreckt.
  11. Verfahren nach einem der Ansprüche 8 bis 10, wobei das Sammelmittel (9) mit einer konstanten oder variablen Lineargeschwindigkeit zwischen den zugeordneten Elektroden (4A, 4B) bewegt wird und/oder sich mit einer konstanten oder variablen Geschwindigkeit um eine vorgegebene oder variable Drehachse in dem dreidimensionalen Raum zwischen den zugeordneten Elektroden dreht.
  12. Verfahren nach einem der Ansprüche 8 bis 11, wobei die Dichte der Mikro-oder Nanofasern, die von dem Sammelmittel aufgefangen werden, durch Variieren einer Relativgeschwindigkeit zwischen den zugeordneten Elektroden und dem Sammelmittel variiert wird.
  13. Verfahren nach einem der Ansprüche 8 bis 12, wobei jede der Elektrospinndüsen wahlweise unterschiedliche Materialien gleichzeitig oder nacheinander einspritzt.
  14. Verfahren nach einem der Ansprüche 8 bis 13, wobei eine Mehrzahl von Elektrospinndüsen an unterschiedlichen Winkelstellungen in Bezug zu einer Drehrichtung der leitenden Elektroden angeordnet sind, um die gleichen oder unterschiedliche faserbildenden Materialien einzuspritzen.
  15. Verfahren nach einem der Ansprüche 8 bis 14, wobei das faserbildende Material aus gelösten und/oder geschmolzenen Polymeren, Keramiken, Metallen und Gemischen aus zumindest zwei der vorgenannten Materialien und/oder unterschiedlichen Vorläuferprodukten oder Gemischen daraus besteht.
  16. Verfahren nach Anspruch 15, wobei die geschmolzenen Mischungen und/oder Lösungen Nanopartikel enthalten.
  17. Verfahren nach Anspruch 16, wobei die Nanopartikel Nanopartikel aus Metallen, Metalloxiden und/oder Keramiken sind.
EP07117780A 2007-10-02 2007-10-02 Vorrichtung und Verfahren für Elektrospinning von 2D- oder 3D-Strukturen von Mikro- bzw. Nanofasermaterialien Not-in-force EP2045375B1 (de)

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