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WO2014120321A2 - Nanofibres auto-cicatrisantes, composites et leurs procédés de production - Google Patents

Nanofibres auto-cicatrisantes, composites et leurs procédés de production Download PDF

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Publication number
WO2014120321A2
WO2014120321A2 PCT/US2013/070110 US2013070110W WO2014120321A2 WO 2014120321 A2 WO2014120321 A2 WO 2014120321A2 US 2013070110 W US2013070110 W US 2013070110W WO 2014120321 A2 WO2014120321 A2 WO 2014120321A2
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Prior art keywords
self
fiber
core
repairing
shell
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WO2014120321A3 (fr
WO2014120321A9 (fr
Inventor
Xiangfa Wu
Arifur Rahman
Zhengping ZHOU
Youhao ZHAO
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North Dakota State University Research Foundation
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North Dakota State University Research Foundation
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Publication of WO2014120321A9 publication Critical patent/WO2014120321A9/fr
Publication of WO2014120321A3 publication Critical patent/WO2014120321A3/fr
Anticipated expiration legal-status Critical
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Classifications

    • 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
    • B29C73/00—Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D
    • B29C73/16—Auto-repairing or self-sealing arrangements or agents
    • B29C73/22—Auto-repairing or self-sealing arrangements or agents the article containing elements including a sealing composition, e.g. powder being liberated when the article is damaged
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D01D5/34—Core-skin structure; Spinnerette packs therefor

Definitions

  • the present invention relates to self-healing nanofibers, composites and methods for manufacturing the same. More specifically, but not exclusively, the present invention relates to a high- strength carbon-fiber/epoxy composite reinforced with self-healing nanofibers and methods for manufacturing the same.
  • a suitable self-healing system should be (i) easily encapsulated and ruptured; (ii) stable and reactive over the entire service life of the polymeric components under various environmental conditions; (iii) responsive quickly to heal damage once triggered; (iv) low cost and low adverse impact on the original material properties [12].
  • the present invention provides self-healing nanofibers, composites and methods for manufacturing the same.
  • the composite may include a bulk constituent and a reinforcing constituent.
  • the composite has one or more interfacial regions, at least one fiber having a hollow core, and one or more self- repairing agents housed in the hollow core.
  • the hollow-core fiber may, for example, be incorporated at the one or more interfacial regions for repairing the composite.
  • Another embodiment provides a method for manufacturing self-repairing composites.
  • the method includes using a fiber collector and a pair of closely spaced conductive wires comprising a dual-wire spinneret.
  • a two-compound emulsion is delivered along the dual-wire spinneret.
  • a voltage is applied between the dual-wire spinneret and the film collector.
  • One or more emulsion jets are ejected from the dual-wire spinneret.
  • a first solution is enwrapped with a second solution from the two-compound emulsion by stretch-forming the second solution under electrostatic force into a core of the first solution.
  • the fiber includes a fiber shell having terminal ends.
  • the fiber shell is formed from a two or more compound solution.
  • a fiber core is enwrapped by the fiber shell at least between the terminal ends.
  • the fiber core is formed from the two or more compound solution.
  • the fiber core includes one or more self-repairing agents.
  • Fig. 1 is a pictorial representation of schematic damage modes in a cross-ply polymer composite in accordance with an illustrative embodiment
  • Fig. 2 is a pictorial representation of hybrid multiscale PMC reinforced with electrospun continuous nanofibers in accordance with an illustrative embodiment
  • Fig. 3 is a pictorial representation of coaxial spinneret, a coelectrospun core-shell DCPD/DMF nanofiber mat and optical micrograph of typical core-shell DCPD/DMF nanofibers in accordance with an illustrative embodiment
  • Fig. 4 is a pictorial representation of a three-point bending test setup and specimens in accordance with an illustrative embodiment
  • Fig. 5 is a pictorial representation of the load-displacement curves of two self- healing specimens in accordance with an illustrative embodiment
  • Fig. 6 is a pictorial representation of SEM micrographs for hybrid multiscale self- healing PMCs in accordance with an illustrative embodiment
  • Fig. 7 is a pictorial representation of other SEM micrographs for hybrid multiscale self-healing PMCs showing dicyclopentadiene release in accordance with an illustrative embodiment
  • Fig. 8 is a pictorial representation of other SEM micrographs for hybrid multiscale self-healing PMCs showing the toughening mechanism in accordance with an illustrative embodiment
  • Fig. 9 is a pictorial representation of a dual-wire emulsion-electrospinning configuration in accordance with an illustrative embodiment
  • Figs. 10-12 are pictorial representations of optical images for emulsion-electrospun core-shell fibers in accordance with an illustrative embodiment
  • Fig. 13 is a pictorial representation of a dual-wire spinneret in accordance with an illustrative embodiment
  • Fig. 14 is a pictorial representation of another dual-wire emulsion-electrospinning configuration in accordance with an illustrative embodiment
  • Fig. 15 is a pictorial representation of a micrographed emulsion in accordance with an illustrative embodiment
  • Fig. 16 is a pictorial representation of a dual-wire emulsion-electrospinning process in accordance with an illustrative embodiment
  • Fig. 17 is a pictorial representation of micrographed core-shell fibers in accordance with an illustrative embodiment
  • Fig. 18 is a pictorial representation of FT-IR spectra for core-shell nano fibers in accordance with an illustrative embodiment
  • Fig. 19 is a pictorial representation of micrographed emulsion-electrospun core- shell fibers in accordance with an illustrative embodiment.
  • Fig. 20 is another pictorial representation of micrographed emulsion-electrospun core-shell fibers in accordance with an illustrative embodiment.
  • the first self-healing system is based on the microencapsulation approach in which microcapsules containing liquid healing agent (healant) and polymeric resin containing catalyst form the constitutive phases of the composite [7,16-25]; the second is based on hollow microfibers containing healing agent [26-33].
  • each self- healing strategy involves incorporation of a healant microcontainer (either microcapsule or hollow microfiber) and a dispersed catalyst within the polymeric resin.
  • the wall of the microcontainers typically with waxy walls
  • the strength of PMCs results from a combined effect of the strength and toughness of the material constituents (i.e., the reinforcing fibers and polymeric matrix), fiber/matrix interfacial properties, microstructure of the composite (e.g., fiber alignment, ply layup, fiber volume fraction, etc.), dominative failure modes, etc.
  • the failure process of a fiber-reinforced PMC laminate is typically a progressive avalanche consisting of microcrack nucleation, matrix cracking, fiber breakage, fiber and matrix debonding, delamination, and final catastrophic failure.
  • the typical damage modes in a cross-ply fiber- reinforced PMC laminate are illustrated in Fig. 1.
  • the actual failure process of a PMC is much more complicated, highly depending upon the types of load, fiber and ply architecture, and physical properties of the constituents, among others.
  • the free- edge delamination-suppression concepts are rooted in altering the singular free-edge stresses near laminate edges [3, 39, 40], while interleaving is based on incorporating discrete thin interlayers of tough plastic resin, particulates, whiskers, or microfibers into the interlaminar regions and therefore enhances the interlaminar fracture toughness, especially in the cases of mode II shearing and impact.
  • an innovative delamination suppression scheme for PMC laminates has been proposed which is based on incorporation of discrete, ultrathin fibers at ply interfaces [41-43].
  • the resulted hybrid multiscale PMC is shown in Fig. 2.
  • the continuous ultrathin reinforcing fibers can be tough plastic polymer nanofibers produced by solution electrospinning [44-49], glass nanofibers [50] by melt
  • this interface toughening technique includes low-weight penalty ( ⁇ 1% in volume fraction), low nanofiber content, and low impact to the processing and global properties of the composite (e.g., specific stiffness, volume fraction of the reinforcing fibers, etc.). Therefore, this toughening technique can be easily integrated into the composite.
  • novel liquid healant- loaded nonwoven core-shell nanofibers are produced by using a low-cost coelectrospinning technique developed recently [53-55] to replace the aforementioned ultrathin nanofibers at ply interfaces (See Fig. 2).
  • the healant-loaded core-shell nanofibers can be entangled into the resin-rich interlayers (with the thickness of tens of microns) between neighboring plies forming ultrathin toughening and self-healing interlayers.
  • these core-shell nanofibers are expected to function as toughening nanofibers [41,49]; moreover, once nanofiber scission happens due to crack-opening and fiber stretching and pull-out induced breakage, the liquid healant will release autonomically at crack fronts under the action of capillary force and then heal the cracks, i.e. result in interfacial self- healing.
  • the liquid healant may vary in viscosity based on ambient conditions. Additives or other considerations are contemplated to allow the liquid healant to flow regardless of the ambient conditions (e.g., cold temperatures). It is also contemplated that the liquid healant may be semi-liquid or have a higher viscosity, including the liquid healant being a gel, wax or other like-viscosity healant.
  • DMF N,N-dimethylformamide
  • a solution of 10 wt% PAN in DMF was prepared to generate the PAN shell material and a solution of 10 wt% DCPD in DMF was prepared to generate the liquid DCPD core.
  • the PAN/DMF solution was prepared by dissolving PAN powder in DMF using a magnetic stirrer installed with a hotplate; the PAN/DMF mixture had been stirred at 80°C for 6 h to form a well-electrospinnable solution.
  • the DCPD/DFM solution was made by dissolving liquid DCPD in DMF using a magnetic stirrer at room temperature.
  • a lab-made coaxial spinneret as shown in Fig. 3(a) was used, which is made up with two coaxially assembled nozzles, pressing plate 1, tightening screws 2, upper nut 3, master tube 4, lower nut 5, seal rube ring 6, and outer nozzle 7 coaxially assembled with the inner nozzle (upper).
  • the outer nozzle has its inner diameter of 0.97 mm, and the inner one carries its outer and inner diameters as 0.71 mm and 0.48 mm, respectively.
  • the PAN/DMF and DCPD/DMF solutions were placed in two 10-ml syringes and connected to the outer and inner nozzles of the coaxial spinneret, respectively.
  • the flow rates of solutions in the outer and inner nozzles were controlled by using two digital syringe pumps (Fisher Scientific Inc., Pittsburgh, PA) such that the flow rate of the outer nozzle (PAN/DMF) was 1.5 ml/h and the flow rate of the inner one (DCPD/DMF) was 1.0 ml/h.
  • a distance of ⁇ 25 cm was fixed between the spinneret outlet and the nanofiber collector, which was a disk-like aluminum plate and electrically grounded.
  • a high DC voltage -18 kV was applied between the spinneret outlet and the nanofiber collector via a positive high- voltage DC power supply (Gamma High Voltage Research, Inc., Ormond Beach, FL).
  • a robust coelectrospinning process could be maintained via tuning the process parameters (e.g., applied DC voltage, flow rates, and distance between the nozzle outlet and nanofiber collector) around the values
  • FIG. 3(b) shows the typical continuous core- shell nanofibers loaded with liquid DCPD as the core material.
  • VARTM vacuum assisted resin transfer molding
  • Epon 862 epoxy resin and Epicure 3234 curing agent were selected as the polymeric matrix for processing the novel PMC in the present work [56].
  • This resin system was purchased from Miller- Stephenson Chemical Company, Inc.
  • the PMC specimens with dimensions: -100 mmx20mm> ⁇ 2.35 mm were cut from the above post-curved PMC laminate (5"x5" x 0.1") using a diamond-tipped rotary saw installed with a water cooling system. Edges of the machined specimens were polished manually using sandpaper to avoid possible pre-damage during the test. Three-point bending test (ASTM- D790) was selected to characterize the flexural stiffness of the novel hybrid multi-scale PMC specimens reinforced with self-healing core-shell nanofibers at interfaces on an Instron machine.
  • Figure 4 shows the three-point bending test setup, in which the span between the two supporting pins was fixed at 75 mm. All the mechanical tests were performed at room temperature with a displacement-control mode such that the loading rate of 5 mm/min was applied. In this study, five specimens were used for evaluation of the self-healing effect in the flexural stiffness recovery after first-ply pre-damage.
  • pre-damage test was first performed by loading the self-healing composite specimens at a constant crosshead speed of 5 mm/min until the first-ply failure happened. Then, the test was stopped and the specimen was unloaded immediately and removed from the testing frame. To simplify the self-healing process for comparison, four specimens after the pre-damage test were heated in a hot press at lOOoC for 1 hr. One specimen was kept as it was after the pre-damage test. Then, all the pre-damaged specimens were post-tested at room temperature using the same testing procedure and control parameters mentioned above.
  • the stiffness recovery rate can be defined as:
  • the initial flexural stiffness is the one of a virgin self-healing PMC specimen subjected to three-point bending load;
  • the healed flexural stiffness is the one of a pre-damaged specimen after first-ply failure, self-healing and then being reloaded in three- point bending test. It is acknowledged that first-ply failure of an angle-ply laminate is due mainly to delamination failure, thus breakage of the healant-loaded core-shell nanofibers at interfaces would release liquid DCPD, which polymerized and healed the interfacial cracks once being triggered by the Grubbs' catalyst in resin.
  • Figure 5 shows the load-displacement curves of two typical self-healing specimens subjected to pre-and post-damage three-point bending loads, respectively. From Fig. 5, it can be founded that the pre-damage load-displacement curves [the solid curves in Figs. 5(a) and 5(b)] corresponding to the first-ply failure are similar to those of common thermosetting carbon- fiber/epoxy PMCs. However, after self-healing of the pre-damaged self-healing PMC specimens, the post-damage load-displacement curves [the dashed curves in Figs. 5(a) and 5(b)] exhibit unique features closely related to the self-healing process.
  • the post-damage tests indicated the nearly complete recovery of the initial flexural stiffness; the healed flexural stiffness was much higher than the residual one after first-ply failure.
  • the healed flexural strength as showed in Fig. 5(a) could reach the flexural strength of the virgin specimen, which is double the residual flexural strength of the pre-damaged specimen after first-ply failure; in Fig. 5(b), the healed flexural strength is -30% higher than the residual flexural strength of the pre- damaged specimen after the first-ply failure though the healed flexural strength is lower than that of the virgin specimen.
  • Fig. 5(b) also indicates that after self-healing, the healed PMC specimen exhibited ductile behavior that could be correlated to the plastic behavior of polymerized DCPD at the healed interfaces. Such interfacial plastic behavior expects to substantially enhance the interlaminar fracture toughness of the self-healing PMC laminates.
  • the healant-loaded core-shell nanofibers can also function to toughen the polymer matrix simultaneously via nanofiber bridging, pull-out, breakage, etc., similar to the toughening mechanisms of solid nanofibers produced by electrospinning as explored in recent studies of interfacial toughening [49-52].
  • the present self-healing technique has its merits.
  • encapsulation of the healing agent to form core-shell nanofibers is based on the low-cost coelectrospinning technique. This process can be conveniently tailored via adjusting the process and material parameters for well uniform fiber diameter and optimized thickness of the nanofiber mats. This technique can also be scaled up for stable and mass production. Note also, that in addition to coelectrospinning, several other cost-effective techniques are contemplated for encapsulation of healing agents into nanofibers and nanotubes via emulsion electrospinning, solution blowing and self-sustained diffusion [55].
  • the present core-shell nanofibers carry the diameters nearly two orders smaller than those based on microcapsules and hollow microfibers as reported recently in the literature [7,16-18,26-28], thus the present self-healing technique can be utilized specifically for localized interfacial toughening and self-healing within a few micrometers, particularly useful to advanced aerospace and aeronautical PMCs which intrinsically bear the weak resin-rich interlayers with the thickness of tens of micrometers.
  • the present disclosure contemplates that such may be interpreted to mean measurements less than one micrometer, or less than lOOnm, or less than a few hundred nanometers.
  • An ultrathin fiber as discussed herein may include measurements (such as, for example a diameter) in the nanometer and micrometer ranges.
  • measurements such as, for example a diameter
  • interfacial toughening and self-healing based on a tiny quantity of continuous core-shell nanofibers at interfaces will not result in an obvious weight penalty and decrease of the superior specific stiffness and strength.
  • core-shell nanofibers can be easily scissored at any location once cracking happens.
  • nanocapsules are difficult to rupture by crack fronts; also, the low volume of healant stored in localized nanocapsules, difficult control of fabrication
  • the present invention also comprises a fiber manufacturing device capable of producing ultrathin continuous core-shell and hollow fibers with a productivity tens to hundreds of times those of existing manufacturing techniques such as coaxial-spinneret based co-electrospinning [58-63] and single-spinneret based emulsion electrospinning [61,62,64].
  • the innovative design of the new device includes two closely spaced parallel thin conductive wires as a spinneret (a dual-wire spinneret) for delivery of two-polymer emulsions (two immiscible polymers dissolved in an organic solvent or similar aqueous two-compound emulsion) along the dual-wire spinneret (See Fig. 9) [65-68].
  • the preparation of the electrospinnable two-polymer emulsion is similar to those used in regular emulsion electrospinning [61,62,64].
  • a high DC voltage is applied between the dual- wire spinneret (connected to the positive electrode) and the fiber collector (connected to the negative electrode)
  • the electrocapiUary effect destabilizes the liquid held between the two parallel wires of the dual-wire spinneret and a conventional Taylor cone (well known to one skilled in the art) cannot be well developed due to the disturbed surface morphology, thus allowing multiple jets to form and eject from the destabilizing droplets on the dual-wire spinneret.
  • one polymer solution enwraps the droplets of the second polymer solution droplets, which depends on the thermodynamics (e.g., the free and surface energy) of the two polymer solutions in the emulsion.
  • the droplets of the second polymer solution After vigorous jet stretching in the electrostatic field, the droplets of the second polymer solution are deformed and stretched significantly to form the core material. After solvent evaporation, the jets deposit on the collector as an ultrathin core-shell fiber mat (see Figs. 10-12).
  • Continuous nanofibers of polymers, carbon, metal oxides, etc. produced by the low- cost top-down electrospinning technique [69] represent a new class of one-dimensional
  • (ID) nanostructured materials that have found extensive applications in protective clothing and wound dressing, [70] filtration, [71] nano fiber composites, [72] scaffolds for tissue growth, [73] drug delivery, [74] energy harvesting, conversion and storage, [75] etc.
  • Electrospinning has also been extended to produce core-shell and hollow nanofibers based on a coaxial spinneret, i.e., coelectrospinning, [76] in which two polymer solutions are utilized to form the core and shell materials, respectively.
  • coelectrospun core- shell nanofibers can be further converted into hollow nanofibers via extracting or thermal decomposition of the core material.
  • Continuous core-shell and hollow nanofibers can be potentially used for gas and liquid transport, drug delivery, electrode materials of supercapacitors and rechargeable batteries, and encapsulation of healing agent for self- healing composites, [77] etc.
  • core-shell nanofibers can also be produced by means of emulsion electrospinning.
  • the core and shell materials are first dissolved separately into solvent to form two immiscible or less miscible solutions. Proper mixture of the two solutions leads to an electrospinnable emulsion.
  • electrospinning of the emulsion droplets of one solution are encapsulated into the electrospinning jet, which are further deformed, elongated, and consequently formed the core of the core-shell fiber. Therefore, emulsion electrospinning can be utilized for producing a variety of core-shell and hollow nanofibers based on the conventional electrospinning setup with a single spinneret, while proper preparation of an
  • a novel dual-wire emulsion-electrospinning method for massive production of ultrathin core-shell polymer fibers is contemplated, in which the emulsion made of one polymer solution droplets merged in the second polymer solution can be delivered via thin liquid film between two closely positioned wires as spinneret (coined as dual-wire spinneret as shown in Fig. 13).
  • the thin liquid film can form a chain of droplets sitting on the dual-wire.
  • the complex morphology of the droplets can facilitate the surface jetting, and the intrinsic capillary force can further drive the emulsion to fill the gap between the two wires as a capillary pump.
  • Figure 14 illustrates the setup of a dual-wire emulsion electrospinning, which consists of a dual-wire spinneret (two closely parallel-positioned copper wires in this study), a rotary metal (aluminum) disk as fiber collector, and two high voltage direct- current (DC) power supplies carrying both the positive and negative voltage outputs, respectively.
  • the use of the DC power supply with a negative voltage output as shown in Fig. 14 is to generate the potential of the fiber collector below the zero potential of all grounded surrounding pieces of equipment and lab utilities and thus to avoid the possible nanofibers flying off the fiber collector during manufacturing.
  • the two closely positioned straight wires function to manipulate and deliver a small quantity of liquid via capillary effect or mechanical motion through an emulsion reservoir.
  • Droplets sitting on a dual-wire spinneret can form either barrel-shaped droplets, which completely enwrap the wire segments, or droplet-bridges, which partially wet the wire segments, depending upon the wetting characteristic curves (W-curves) of the system.
  • the electrocapiUary force acting on the liquid-bridge can easily destabilize the liquid-bridge and form multiple droplets as shown in Fig. 14(a); each droplet initiates one or multiple jets as shown in Fig. 14(b) due to the complex morphology of the droplets.
  • the electrocapillary force can drive the emulsion to the jetting zone [Fig. 14(b)].
  • the pumping process can also be realized via moving the dual-wire forth and back through the emulsion reservoir (mechanical translation).
  • the use of dual-wire spinneret can significantly suppress the fast evaporation of the volatile solvent through reduction of the exposure of the emulsion to open air.
  • an emulsion was prepared via blending 10 wt. % polyacrylonitrile (PAN)/N,N-dimethyl formamide (DMF) and 10% isophorone diisocyanate (IPDI)/DMF solutions with the mass ratio 1 : 1 and tested on the basis of the proof-of-concept setup with varying parameters (See
  • Fig. 15 shows the snapshots of emulsion electrospinning of one emulsion droplet sitting on the dual-wire spinneret with increasing DC voltage between the wires and the fiber collector.
  • Figure 17 shows the typical optical micrographs of the ultrathin core-shell
  • IPDI/PAN fibers produced by the proposed dual-wire emulsion electrospinning setup, in which the diameter of the two identical copper wires is 0.28 mm and the wire spacing is 0.30 mm. It can be found from Fig. 17 that the core-shell fibers were well formed with uniform morphologies of the interior liquid IPDI core and exterior solid PAN shell. In this case, multiple measurements show that the average diameter of the IPDI core is 0.41 ⁇ and the average exterior diameter of the PAN shell is ⁇ . ⁇ . In addition, FT-IR was further used to validate the chemical composition of PAN/IPDI nano fibers.
  • Figure 18 gives the comparison of FT-IR spectra between pure PAN nanofibers and PAN/IPDI core-shell fibers, which confirms the existence of IPDI in the core-shell fibers.
  • the characteristic absorption bands at 2920 cm-1, 2238 cm-1, 1662 cm-1 and 1449 cm-1 are assigned to v C - H stretching, v C ⁇ N stretching, 5C - H bond bending and 5CH2 asymmetry, respectively.
  • FIG. 19 shows the typical optical micrograph of the core-shell IPDI/PAN fibers. It can be observed that though the core-shell PAN/IPDI fibers had been well formed with smooth morphologies of the interior core and exterior shell, the diameter of the core-shell fibers had a large variation. Multiple measurements show that the average diameter of the IPDI core is 0.72 ⁇ and the average diameter of the PAN shell is 1.95 um, which are much larger than those based on the dual-wire spinneret with the wire spacing of 0.30 mm.
  • Figure 20 shows the typical optical micrograph of the core-shell PAN/IPDI fibers. From Fig. 20, it can be found that the core-shell PAN/IPDI fibers still carried well-formed morphologies of the interior core and exterior shell.
  • the diameter of the core-shell fibers had a much larger variation than those in the above two cases.
  • the average diameter of the IPDI core is 0.78 ⁇ and the average diameter of the PAN shell is 2.02 ⁇ , slight larger than those based on the dual- wire spinneret with zero spacing. Therefore, the dual-wire spinneret is expected to offer a flexible manner to tailor the geometries of electrospun core-shell fibers.
  • liquid isophorone diisocyanate IPDI
  • DMF ⁇ , ⁇ -dimethyl formamide
  • the experimental setup is illustrated in Fig. 14 and characterized by a dual- wire spinneret of two parallel copper wires fixed on a metal fixture, a lab-made rotary aluminum disk (diameter: 25 cm and thickness: 2.5 mm), and two high voltage DC power supplies (Gamma High Voltage Research, Ormond Beach, FL) with the positive and negative voltage outputs, respectively.
  • the rotary disk is placed parallel to the two-wire plane with a vertical distance ⁇ 30 cm and powered by a DC electrical motor with adjustable angular velocity.
  • copper wires with two different diameters (0.28 mm and 0.78 mm) and two different values of spacing (0 mm and 0.30 mm) were selected for the dual-wire spinneret.
  • the dual-wire emulsion-electrospinning test was performed at room temperature.
  • the two wires of the spinneret were cleaned with acetone to maintain largely constant surface energy of the wires.
  • the emulsion was first delivered to the spinneret manually for form multiple droplet-bridges as illustrated in Fig. 14.
  • multiple jets initiated from each droplet bridge as illustrated in Fig. 15.
  • the obtained ultrathin core-shell PAN/IPDI fibers were characterized using an optical microscope (IX 71 Olympus with the objective magnification 40).
  • the present invention is not to be limited to the particular embodiments described herein.
  • the present invention contemplates numerous variations in the type of ways in which embodiments of the invention may be applied to [Insert high-level or more detailed description of the invention].
  • the foregoing description has been presented for purposes of illustration and description. It is not intended to be an exhaustive list or limit any of the disclosure to the precise forms disclosed. It is contemplated that other alternatives or exemplary aspects that are considered included in the disclosure.
  • the description is merely examples of embodiments, processes or methods of the invention. It is understood that any other modifications, substitutions, and/or additions may be made, which are within the intended spirit and scope of the disclosure. For the foregoing, it can be seen that the disclosure accomplishes at least all of the intended objectives.

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  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
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  • Artificial Filaments (AREA)

Abstract

Cette invention concerne un nouveau type de composites hybrides à base de fibres de carbone/époxy ayant une résistance mécanique élevée renforcés par des fibres cœur-coque renforçantes et auto-cicatrisantes ultraminces aux interfaces au moyen d'une technique de superposition par voie humide, suivie d'un moulage par transfert de résine assisté sous vide (VARTM). Les fibres cœur-coque chargées d'agent cicatrisant (monomère liquide à température ambiante) sont produites par un co-filage électrostatique qui consiste à utiliser une solution de polymère de type plastique (dissous dans un solvant organique) à titre de jet extérieur et la solution de monomère à titre de jet intérieur. Un dispositif de fabrication de fibres utilisant une nouvelle méthode de filage électrostatique d'émulsion à double fil, capable de produire des fibres cœur-coque et creuses ultraminces à des volumes commerciaux est en outre décrit.
PCT/US2013/070110 2012-11-14 2013-11-14 Nanofibres auto-cicatrisantes, composites et leurs procédés de production Ceased WO2014120321A2 (fr)

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WO2018099910A1 (fr) 2016-11-29 2018-06-07 Advanced Materials Design & Manufacturing Limited Procédé de fabrication de textiles hybrides (en fibres-nanofibres) par l'intermédiaire de liaisons efficaces de fibres à nanofibres comprenant de nouveaux mécanismes de transfert de charge efficaces
EP3412801A1 (fr) * 2017-06-09 2018-12-12 Technische Universität Graz Procédé de production d'un agencement régulier de gouttelettes d'un premier liquide en jet continu d'un second liquide
CN108232027A (zh) * 2017-12-27 2018-06-29 青岛海信电器股份有限公司 图形化柔性电极及制备方法、柔性显示装置
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CN116536784A (zh) * 2023-06-15 2023-08-04 南通大学 一种光响应性自修复纳米纤维及其制备方法

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