KR20170072551A - Manufacturing method for composite fiber and manufacturing method for composite fiber assembly using the same and composite fiber assembly made by the same - Google Patents
Manufacturing method for composite fiber and manufacturing method for composite fiber assembly using the same and composite fiber assembly made by the same Download PDFInfo
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- KR20170072551A KR20170072551A KR1020150180842A KR20150180842A KR20170072551A KR 20170072551 A KR20170072551 A KR 20170072551A KR 1020150180842 A KR1020150180842 A KR 1020150180842A KR 20150180842 A KR20150180842 A KR 20150180842A KR 20170072551 A KR20170072551 A KR 20170072551A
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- D—TEXTILES; PAPER
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- C01B31/022—
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- 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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B1/00—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B3/00—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/003—Treatment with radio-waves or microwaves
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/49—Oxides or hydroxides of elements of Groups 8, 9, 10 or 18 of the Periodic System; Ferrates; Cobaltates; Nickelates; Ruthenates; Osmates; Rhodates; Iridates; Palladates; Platinates
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/61—Polyamines polyimines
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F41—WEAPONS
- F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
- F41H1/00—Personal protection gear
- F41H1/02—Armoured or projectile- or missile-resistant garments; Composite protection fabrics
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/06—Load-responsive characteristics
- D10B2401/062—Load-responsive characteristics stiff, shape retention
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2501/00—Wearing apparel
- D10B2501/04—Outerwear; Protective garments
Abstract
The present invention relates to a process for the surface treatment of a fiber material to produce carboxylic acid groups on the surface of the fiber material, a step of mixing a polypyrrole (PPy) or a mixture of polypyrrole and graphene oxide (GO) A step of coating the fiber material with a catalyst metal aqueous solution, and a step of growing columnar carbon nanotubes on the surface of the fiber material by irradiating the fiber material with microwaves.
Therefore, since the thickness can be made thinner while satisfying the required rigidity, it is possible to improve the feeling of fit by being flexible.
Description
The present invention relates to a method for producing a composite fiber, a method for manufacturing a composite fiber body using the same, and a composite fiber body manufactured by the method. More particularly, the present invention relates to a composite fiber having a thin thickness, And a composite fiber body produced by the method.
Body armor is a product that uses bulletproof material and protects people from bullets. It should first be light in weight, have good shot and heat shock resistance, and have a small structural strain.
Therefore, it is desirable that the fiber used in such a body armor has high strength, high elasticity, high heat resistance and low specific gravity, and conventionally, a high strength polyethylene sheet or a ceramic plate and aramid fabric A laminate of laminated aramid fabric laminate is laminated to each other.
However, the fiber material used in the above-described conventional body armor needs to be thick in order to have a high manufacturing cost, difficulty in manufacturing, required rigidity, and rigidity, and is not heavy and flexible, there was.
Disclosed is a method for producing a composite fiber which is light and flexible because of its high strength and can be made thin, a method for producing a composite fiber body using the same, and a composite fiber body manufactured by the method.
According to one aspect of the present invention, there is provided a method for producing a polyester fiber, comprising the steps of: surface treating the fiber material to produce carboxylic acid groups on the surface of the fiber material; forming polypyrrole (PPy) A step of coating a mixture of Graphene oxide (GO), a step of immersing the fiber material in a catalyst metal aqueous solution, and a step of growing columnar carbon nanotubes on the surface of the fiber material by applying microwaves to the fiber material The present invention also provides a method for manufacturing a composite fiber including the composite fiber.
According to another aspect of the present invention, there is provided a method for producing a carbon nanotube, the method including: forming columnar carbon nanotubes on the surface of a fiber material; laminating the plurality of fiber materials so as to be spaced apart from each other; And a step of combining the fibrous materials.
According to still another aspect of the present invention, there is provided a fiber-reinforced composite material comprising: a plurality of fiber materials stacked in a vertical direction with a space therebetween, the fibers being formed on the upper and lower surfaces of the fiber material, And a resin layer filled in the space to bond the fiber materials so that the carbon nanotubes and the carbon nanotubes are impregnated.
The composite fiber body according to the present invention, the composite fiber body using the composite fiber body, and the composite fiber body manufactured by the method provide the following effects.
First, by growing carbon nanotubes on the surface of a fibrous material so that the composite fibers possess the characteristics of carbon nanotubes, they can be used as various kinds of special fibers.
Second, since a plurality of fiber materials in which carbon nanotubes are grown are laminated and a resin is filled therebetween, high rigidity can be maintained.
Third, since it has a high rigidity and tensile strength, it can be thinned when applying special fibers such as a bodyshirt, so that it can be manufactured lightly by reducing weight, and can be flexibly improved by wearing.
Fourth, since it has excellent mechanical strength and electrical conductivity, it can be used in special textile field which can shield electromagnetic interference.
Fifth, since expensive devices such as a separate inert gas shielding device for growing carbon nanotubes are not needed, it is economical and can facilitate the synthesis of carbon nanotubes as well as inducing rapid growth of carbon nanotubes in time. can do.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart showing a process of a method for manufacturing a composite fiber according to an embodiment of the present invention; FIG.
FIG. 2 is a perspective view showing the composite fiber produced by the composite fiber manufacturing method of FIG. 1; FIG.
3 is a flow chart showing a process of a method for manufacturing a composite fiber body according to an embodiment of the present invention.
4 is a cross-sectional view showing a composite fiber body manufactured by the composite fiber body manufacturing method of FIG.
5 is a view showing a manufacturing process of the composite fiber manufacturing method of FIG.
FIG. 6 is a graph showing Raman spectra according to the surface treatment of a fiber material in the composite fiber manufacturing method of FIG. 1. FIG.
FIG. 7 is a SEM photograph showing growth of carbon nanotubes according to a coating treatment method in the composite fiber manufacturing method of FIG. 1; FIG.
FIG. 8 is a TEM photograph showing carbon nanotubes grown after microwave irradiation in the composite fiber production method of FIG. 1. FIG.
FIG. 9 is a graph showing X-ray diffraction analysis of the composite fiber produced by the composite fiber production method of FIG. 1; FIG.
10 is a graph showing the FTIR spectra of the composite fibers produced by the composite fiber production method of FIG.
11 is a graph showing the thermogravimetric characteristics of the conjugate fiber produced by the conjugate fiber production method of FIG.
12 is a graph showing tensile strength characteristics of the composite fibers produced by the composite fiber production method of FIG.
13 is a graph showing shear stress characteristics of the composite fibers produced by the composite fiber production method of FIG.
FIG. 14 is a graph showing energy and speed characteristics of the composite fiber produced by the composite fiber manufacturing method of FIG. 1 over time. FIG.
15 is a graph showing electrical conduction characteristics of the composite fibers produced by the composite fiber production method of FIG.
FIG. 16 is a graph showing the spectral characteristics of the graphite nanomolecules in the composite fibers produced by the composite fiber production method of FIG. 1; FIG.
FIGS. 17 and 18 are graphs showing X-ray diffraction analysis of graphite nanomolecules in the composite fiber produced by the composite fiber production method of FIG.
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
Referring to FIGS. 1 and 2, a method of fabricating a composite fiber according to an embodiment of the present invention includes growing a
First, the
The
In detail, the surface treatment of the
The basic treatment of the
After the
When the
When the surface of the
Meanwhile, since the coating process is performed on the basis of the polypyrrole and the graphene oxide as described above, the cost of the composite fiber can be reduced and the coating time can be shortened. Therefore, the conventional chemical vapor deposition process is technically Limit can be solved.
Then, the
Meanwhile, although the composite fiber has been described as an example in which a catalytic metal is used to synthesize and grow the carbon nanotube, if the carbon nanotubes can be synthesized in addition to the catalyst metal method described above, various methods Of course, it is applicable.
After the surface treatment and coating are completed, carbon nanotubes (CNTs) 30 are grown on the surface of the
The
Although the
3 is a flow chart showing a process of a method for manufacturing a composite fiber body according to an embodiment of the present invention. Referring to the drawings, the method for fabricating a composite fiber body includes the steps of forming (S210) columnar carbon nanotubes (200) on the surface of a fiber material (100) (S220), and filling the fiber material (100) by filling (S230) resin between the fiber materials (100).
First,
After the
When the
4, when the
After the
4 is a cross-sectional view showing a composite fiber body produced through the above-mentioned method for producing a composite fiber body. Referring to the drawings, the composite fibrous body includes a plurality of
According to the above description, the composite fiber body has a structure in which a plurality of
(Example)
Carbon nanotubes are a new class of functional materials with many properties that are superior to typical polymeric composites in mechanical properties, low density, and unusual physical and chemical properties. Carbon nanotubes can be fabricated with high-ratio nanotubes to enhance the polymer matrix to produce high-performance polymer composites. The maximum strengthening effect of carbon nanotubes is not effective because the van der Waals force between the nanotubes agglomerates at high loading friction. Directly increasing carbon nanotubes on the surface of the fibers increases the surface area for interaction and eliminates the diffusion of foreign matter in high loading friction. In addition, the stress transfer between the polymer matrix and the entangled fibers is enhanced by mechanically consolidating and partially reinforcing the carbon nanotubes on the fiber surface. Various synthetic methods have been developed to produce carbon nanotubes including flat plate culture, chemical vapor deposition (CVD), arc discharge, and lithography. These techniques require inert gas shields and expensive equipment and are time consuming. Unlike CVD and other synthesis methods, carbon nanotube microwave induced synthesis does not generate an inert gas atmosphere and does not require complex experimental setups. This technology is economical and can produce carbon nanotubes in 15 to 30 seconds. By growing carbon nanotubes with zero-dimensional metal nanoparticles on the fiber surface at the fiber surface, a special reinforced nanomaterial can be created that can be used to produce composites with unprecedented performance.
Kevlar fiber, which has mechanical and high strength performance, is used in many high performance equipment, especially in bulletproof vests and aviation industry as a structural composite material. The synthesis of carbon nanotubes on the surface of Kevlar fibers allows the fibers to have both mechanical strength and electronic conductivity. Electrically conducted Kevlar composites can be used as EMI (electromagnetic interference) shields in airplanes, spacecraft, and communications devices. However, since Kevlar is an insulating material, it is impossible for carbon nanotubes to directly grow on Kevlar fibers. Thus, the keel fiber is coated with the conductive polymer. The coated fiber can be heated to very high temperatures for a very short period of time. When heated to 1,100 to 1,200 DEG C, the conductive polymer is converted into graphite nanocarbon, thereby providing a revolutionary method for synthesizing carbon nanotubes through microwave irradiation. Oxidized nanoparticles - carbon nanotubes grown on the surface of Kevlar fibers convey multifunctional performance to the resulting hybrid compounds.
Graphene has excellent mechanical properties and excellent electrical conductivity, but interacts very weakly with the polymer matrix. The oxidation of graphene, ie graphene oxide (GO), enhances the mechanical properties of the composition to a noticeable extent. The reactive functional groups, carboxylic acid, epoxy, and hydroxyl groups on the GO sheet surface, increase the interfacial interactions between polymer functional groups and fiber functional groups. GO is known to have electrical insulation properties, but it also has excellent thermal conductivity of 3,500 to 5,300 Wm-1K-1.
Here, a metal nanomolecule-carbon nanotube is synthesized on the surface of a woven kevlar fiber (WKF) using a microwave induction method. The entire process takes only 15-30 seconds. The surface of WKF was functionalized with carboxylic acid and primary amine groups through the rupture of the amide bound to the existing properties of the polymer chain surface of the base fiber. This surface treatment increased the degree of interaction between functional groups of polypyrrole and oxidized graphene. The WKF surface was coated with conductive polypyrrole and oxidized graphene / polypyrrole through in situ polymerization. The coated WKFs were mixed with a ferrocene-toluene solution. As soon as the microwave was irradiated, the conduction layer quickly developed and exceeded 1,100 ° C and spark and electric arc occurred. Through this investigation, ferrocene is decomposed into an iron catalyst and a cyclopentadienyl ring, which acts as a carbon source for increasing carbon nanotubes, is produced. 5 is a schematic view showing that iron-carbon nanotubes are grown after microwave irradiation in a woven Kevlar fiber. WKFs with iron-carbon nanotubes were used to make composites with vacuum assisted resin transfer mold technology with polyester resin (PES). The effects of iron carbon nanotubes on impact reaction, tensile strength, in - plane shear force, and electrical conductivity of composites were investigated. The properties of composites containing iron - carbon nanotubes grown from polypyrrole (PPY) and PPY / GO coated WKF were compared.
a. material
Woven Kevlar fibers (grade A-200), sodium hydroxide (NaOH), potassium permanganate (KMnO 4 ), and concentrated sulfuric acid (H 2 SO 4 ) purchased from JMC were purchased from Samcheon Pure Chemical Co., Ferrocene, pyrrole, iron chloride hexahydrate (FeCl 3 6H 2 O), N-methylprolitone (NMP), toluene, and hexane were purchased from Sigma-Adrich. Reagent grade Sodium nitrate (NaNO 3 ) and hydrogen peroxide (H 2 O 2 ) were purchased from Duksan Pure Chemical. Ethanol was obtained from JT Baker and used as received.
b. WKF Surface Treatment
WKF samples acetone to eliminate microbial contamination-cut after the rinse with ethanol mixture, 75 X 75-mm 2 square. The sample was dried in an oven, immersed in a 10% solution of sodium hydroxide and allowed to stand at room temperature for 30 minutes. The treated samples were washed several times with demineralized water and then dried in an oven at 90 ° C for 1 hour. The oven-dried samples were immersed in a 10-N aqueous hydrochloric acid solution for 10 seconds. The sample was taken out, washed several times with water, and dried at 90 ° C for 1 hour. Since the sample was immersed in a hydrochloric acid solution, excess metal ions on the fiber surface were removed. Carbonic acid group was formed by ion exchange reaction in place of hydrogen ion in place. This carboxylic acid group interacts with the hydroxyl carboxylic acid group and the epoxy group in the oxidized graphene.
c. Graphene oxide synthesis
The oxidized graphene was made from graphite nanoparticles by a modified Hummer method. Five grams of graphite nanoparticles were dispersed in 5 g of NaNO 3 and 300 mL of concentrated H 2 SO 4 . The reaction mixture was placed in an ice bath and kept at a temperature of 15 ° C or lower. 30 g of KMnO 4 was slowly added while stirring. The temperature was added for 2 hours while keeping the temperature below 15 < 0 > C. The reaction vessel was immersed in a water bath at 35 DEG C for 30 minutes, and then 200 mL of water at 70 DEG C was added dropwise to the reaction vessel. Due to this, the reaction mixture reached 98 ° C and was stirred for an additional hour. 700 mL of water at 70 DEG C was further added, and then 100 mL of 30 wt% hydrogen peroxide was added. The reaction was again purged for 1 hour. The reaction mixture was centrifuged and the resulting material was washed until the pH was neutral. By doing so, we were able to eliminate unnecessary acid and inorganic salts. The resulting graphite oxide powder was dried at 45 ° C for 48 hours in a vacuum oven. Then, it was put into distilled water and ultrasonicated by stirring. This was the process of peeling the graphite powder to become graphene oxide, and the solution was centrifuged. The collected materials were finally dried at room temperature.
d. WKF phase pyrrole or pyrrole / oxidized graphene deposition via in situ oxidative polymerization
The pyrrole solution (12% v / v) is made up of methanol and water 50:50. WKF was placed in this solution containing the ultrasonic generator and kept at room temperature for 60 minutes. WKF was taken out of the solution, placed in FeCl 3 (12% w / v) aqueous solution (oxidizing agent) and immersed for 15 minutes to complete the polymerization reaction. The polypyrrole-coated WKF thus obtained was washed several times with demineralized water and then dried in an oven at 60 ° C overnight. To prepare polypyrrole / oxidative graphene coated WFK, the oxidized graphene was first dispersed in NMP and sonicated for 1 hour. The pyrrole monomer (12% v / v) was added to the oxidized graphene dispersion in NMP. The WKF was then dipped in the pyrrole solution and sonicated in a 25 ° C water bath for 60 minutes. NMP is used as a solvent because it can blow Kevlar and is a good solvent for the dispersion of oxidized graphene. Due to these properties, deposition of oxidized graphene / polypyrrole on the WKF surface was better. The sample was then transferred to an aqueous FeCl 3 solution (12% w / v) for 15 minutes, and finally the fibers were taken out and washed and dried in the oven overnight.
e. Carbon nanotube microwave induced growth
The coated sample was mixed with a prepared ferrocene solution prepared by dissolving a large amount of ferrocene in toluene and immersed in an ultrasonic working bath for 15 minutes. This is because the ferrocene was uniformly dispersed among the samples. Samples of ferrocene were evaluated at three weight ratios of 1: 1, 1: 0.5, and 1: 0.1. To enhance carbon nanotube growth on the substrate surface, 0.25 mL hexane was added. The sample was microwaved in a home microwave oven after partial evaporation of solvent in air for 1 minute. Samples containing iron-carbon nanotubes were prepared to make composites with PES by the VARTM process.
f. Characterization
Raman spectra were used as a backscattering geometry through a micro-Raman microscope using a 532-nm stimulus laser. The polarizer was placed parallel to the analyzer. Growth of iron-carbon nanotubes on WKF surface was investigated using Nova NanoSEM 230 operating at 15 kV. The synthesis of carbon nanotubes was confirmed by HR-TEM analysis. Diffraction was determined at a 40 kV voltage using a 5 ° to 80 ° (2θ) Cu-Kα radiation of a crystal monochromated 20-mA current using a wide-angle X-ray diffractometer. FT-IR studies were performed with a spectrophotometer at 4,000-500 cm -1 . The temperature stability of the sample and the growth of the iron-carbon nanotubes on the WKF surface were determined by data collected in a thermogravimetric analyzer (TGA). The TGA was operated at a rate of 10 [deg.] C / min up to 1,200 [deg.] C under a nitrogen atmosphere. An Instron 5982 universal testing machine was used for tensile testing of the samples at a maximum load of 100 kN and a displacement rate of 2 mm / min. The experiment was performed three times per each sample according to ASTM D3039. Shear reaction of WKF composites was carried out at +45 섬유 in direction of fiber relative to tensile strength. Impact test according to ASTM D5628-10 was performed using a drop impact tester. The diameter of the circular clamp was 40-mm and had a 5-kg impactor. Data was obtained between the initial impact contact point and the transit point, which was determined to be 100 J, which is the fully penetrated state of the samples. Electrical conduction experiments were performed with a 6517 Multimeter.
The Roman spectrum of graphite nanomolecules contains one band at 1,350 cm < -1 > corresponding to the D band. As shown in Fig. 16, a large and sharp G band appears at approximately 1,587 cm < -1 > because of the structural defects and the E2g method of black-and-white sculpture. The shape of the G 'band at 2,714 cm -1 is associated with defects in graphite fragments. The formation of oxidized graphene has resulted in an increase in the intensity ratio (ID / IG) between the D and G bands. The ID / IG ratio increased as a result of defects due to the presence of several functional groups that interfere with orientation immediately upon conversion to oxidized graphene. The roman spectra of iron-carbon nanotubes grown in WKF is shown in Fig. The peaks found in the WKF spectrum are well matched with those reported in the literature. The in situ polymerization of pyrrole at the surface of WKF marks the peak at 937 and 937 cm -1 associated with the quinoid bipolarolone and polaron structures of polyphenols. The bands at 1,061 and 1,111 cm -1 are due to the -CH extension. The spectra of WKF samples deposited with polypyrrole and oxidized graphene show the apex characterized by polypyrrole. The peak at 1,326 and 1,575 cm -1 was slightly increased by the D and G bands of the oxidized graphene and a new peak was observed at 2,665 cm -1 due to the G 'band of the oxidized graphene. The growth of iron-carbon nanotubes on the surface of the polypyrrole-coated or oxidized graphene / polypyrrole-coated WKF further enhanced the strength between the D and G bands while the apex at 2,665 cm -1 became more prominent. The same intensities of D and G bands mean that the carbon nanotubes are multi-walled. Figure 6 shows the spectra of iron-carbon nanotubes grown in WKF, polypyrrole coated WKF, oxidized graphene / polypyrrole coated WKF, polypyrrole coated WKF, and iron-carbon nanotubes grown in oxidized graphene / polypyrrole coated WKF .
Figure 7 shows a SEM micrograph of the growth of iron-carbon nanotubes after polypyrrole coating, WKF coated with polypyrrole / oxide graphene, and microwave irradiation. WKF has a smooth surface while the polypyrrole-coated WKF is completely rough than the surface shape of the top WKF. Polypyrrole is clearly visible on the fiber surface. Oxidation graphene / polypyrrole coating The micrograph of WKF shows an oxidized graphene sheet embedded with polypyrrole and attached to the fiber surface. The electrostatic interaction between the negative charge of the oxidized graphene and the negatively charged pyrrole as well as the π-π interaction between the oxidized graphene complex bond and the pyrrole ring enables the polymerization reaction of pyrrole on the surface of the oxidized graphene sheet do. The pyrrole has a large surface area of the oxidized graphene sheet and thus has sufficient area for polymerization. Therefore, the oxidized graphene acts as a structural composite with a thin coating of polypyrrole. Exposure of polypyrrole coated WKF mixed with ferrocene (1: 1), toluene, and hexane to microwave irradiation promotes the dense growth of iron-carbon nanotubes on the fiber surface. The fiber was surrounded by carbon nanotubes with iron nanomolecules running at the ends and randomly oriented as shown in the micrograph of FIG. 3d. Polypyrrole absorbs microwave radiation, causing the ferrocene molecules to decompose into free iron atoms and two cyclopentadienyl (C 5 H 5 ) rings, resulting in rapid temperature increase. Iron nanomolecules are formed by condensation of iron atoms that are still in a molten state. The cyclopentadienyl group, toluene, and hexane are used as carbon sources and are dispersed across the surface of the substrate and iron nanomolecules. After the carbon atoms are precipitated from the iron nanomolecules to form a graphite film on their own, the nanotubes grow. Microphotographs of oxidized graphene / polypyrrole coated samples after 15 - 30 second microwave irradiation with ferrocene (1: 1), toluene, and hexane showed that carbon nanotubes on the fiber surface were similar with iron nanomolecules at the ends (Fig. 7 (e)). The growth of iron-carbon nanotubes depends on the concentration of ferrocene in the growth solution. When the ratio of ferrocene to substrate was changed from 1: 0.5 to 1: 0.1, the density of the fibrous iron-carbon nanotubes and the thickness of the carbon nanotubes, that is, the inner diameter of the nanotubes were reduced (FIG. - (f)). On the other hand, referring to the SEM photograph of FIG. 7, (a) is a WKF, (b) is a polypyrrole-coated WKF, (c) is a graphene / polypyrrole coated WKF, (E) represents iron-carbon nanotubes grown on an oxidized graphene / polypyrrole coated WKF (1: 1, substrate: ferrocene), and (f) represents carbon nanotubes grown on a graphene / polypyrrole Carbon nanotubes grown on coated WKF (1: 0.5, substrate: ferrocene) and (g) represent iron-carbon nanotubes grown on oxidized graphene / polypyrrole coated WKF (1: 0.1, substrate: ferrocene) . On the other hand, the photographs inserted into the upper right side of the photograph are high-resolution microscopic photographs of carbon nanotubes with iron molecules attached to their heads.
Referring to the TEM micrograph of FIG. 8, the iron-carbon nanotubes grown in polypyrrole-coated WKF and oxidized graphene / polypyrrole-coated WKF are clearly multi-walled carbon nanotubes. In both cases, the iron nanomolecules are encapsulated between the ends of each nanotube and the nanotubes. This is why the inner diameter of the nanotubes decreases as the ferrocene concentration decreases. Iron nanomolecules accumulate between nanotubes. The capillary effect created during the growth of carbon nanotubes from the graphite membrane results in the first molten iron nanomolecules being embedded between the nanotubes. The viscosity of the iron nanomolecules, including the motions of the carbon nanotubes, the balance between the various forces, the frictional force between the inner wall of the existing carbon nanotube and the built-in iron nanomolecules, and the iron nanomolecules Are the factors that determine the location of the iron nanomolecules inside the nanotubes. In some cases, the molten catalyst molecules have a rectangular shape within the nanotubes rather than being encased in small pieces (Fig. 8 (b)). On the other hand, FIG. 8 is a TEM micrograph of iron-carbon nanotubes synthesized in (a) and (b) polypyrrole-coated WKF and (c) oxide graphene / polypyrrole-coated WKF after microwave irradiation.
In the X-ray diffraction diagram, the graphite nano-plate shows a strong and sharp peak at 2? = 23.7 ° due to the (002) plane. In the oxidized graphene, this peak shifted by 10.35 ° and a broad peak appeared at 17.03 ° as shown in Fig. The wide apex shape is due to the presence of various oxygen containing functional groups on the oxide graphene surface. These groups cause the oxidized graphene sheet to loosely deposit, thereby increasing the space between the oxidized graphene sheet layers. 9 is an X-ray diffraction pattern of iron-carbon nanotubes grown on WKF, coated WKF, and WKF, after microwave irradiation. WKF shows strong diffraction peaks at 2θ = 20.64 ° and 23.19 ° corresponding to (110) and (200) plane, respectively. The degree of rotation of pure pyrrole has a wide peak between 20 ° and 25 °. The increase in strength of the polypyrrole-coated WKF occurs at the peak at 2θ = 20.90 ° and 23.67 °, because the apex in the WKF diffraction pattern meets the apex in the pure polypyrrole. The diffraction peak due to the (002) graphite surface of the graphene oxide was observed in the diffraction pattern of the graphene / polypyrrole coated WKF. In addition, the peaks corresponding to the (110) and (200) plates also increased in strength. The growth of iron-carbon nanotubes on the surface of the polypyrrole coated WKF was confirmed by the peaks observed at 41.41 ° C (100 °), 43.32 ° (Fe3C), 44.52 ° (Fe) and 53.76 ° (
The FTIR study showed that as shown in FIG. 18, the 3,329 cm -1 (-NH extension), 2,926 cm -1 (-CH 2 asymmetric extension), 2,845 cm -1 (-CH 2 symmetrical extension), 1,651 cm -1 C = O extension), 1,312 cm -1 (CH 2 strain), 1,109 cm -1 (CN expansion), 985cm -1 (aryl CH-plane vibration), and the non-treated at 820 cm -1 (CH out-of-plane refractive) WKF appears as absorption bands. The surface functionalization of WKF is confirmed by the width of the peak at 3,329 cm -1 due to the -OH extension of the carboxylic acid group and the -NH extension of the amine group. The -OH refractive vibration of the carboxy group makes the apex more noticeable at 1,405 cm -1 . Vertex intensity was found at 1,108 cm -1 (CN extension). After surface treatment, the carboxylic acid and the main amine group developed on the WKF surface through the curvature of the amides connected to the backbone of the surface polymer chain, and the intensity of the peak corresponding to the CN bond extension was decreased. In the FTIR study of surface-functionalized aramid fibers, Ehlert et al. A similar discovery has been reported. The spectra of the polypyrrole-coated samples were 1,652 cm -1 (C = O aramid extension), 1545 and 1,455 cm -1 (asymmetric and symmetrical ring extension of polypyrrole), 1,295, 1,088
The degree of mechanical enhancement that can be provided by the iron-carbon nanotubes in the WKF composite was estimated in Figures 12 (A) and (B), which represent the stress-strain curves and the tensile strength and modulus of the composite. Compositions coated with polypyrrole and oxidized graphene / polypyrrole are mechanically stronger than the man WKF / PES composites. The grafting of oxidized graphene with polypyrrole appeared in the upper surface area and increased the degree of interaction between oxidized graphene sheet, polypyrrole, WKF and PES. As a result, the mechanical strength was further increased. Thanks to the oxidized graphene sheet, the pressure transfer from the polymer to the fiber was good when external pressure was applied. In addition, functional groups on the surface of oxidized graphene interact well with the carboxylic acid and amine groups of the functionalized WKF. The interaction of polypyrrole with π-π laminated with oxidized graphene, and with the carboxylic acid group of WKF, enhanced the adhesion of polypyrrole and oxidized graphene on the WKF surface. The upper non-surface areas of the coated fibers, the geometric structure of the wrinkled and planar graphene graphene, and the bridges of the pendant functional group resulted in occlusion with polypyrrole and PES chains.
The synthesis of iron-carbon nanotubes occurring on the surface of polypyrrole or oxidized graphene / polypyrrole-coated fibers after microwave irradiation also improved the mechanical properties of the synthesis result. The addition of iron-carbon nanotubes created a network structure within the composite. This effectively increased the interaction between the polymer and the fiber and enhanced the efficiency of load transfer from the polymer. Fixing iron nanomolecules at the ends of the nanotubes was a result of widening the interaction area. Iron nanomolecules certainly increased the mechanical performance of a given synthetic material. The synthesis of iron-carbon nanotubes on oxidized graphene / polypyrrole coated WKF increased tensile strength and modulus by 122.57% and 89.82%, respectively. The same process on polypyrrole coated WKF also resulted in 105.41% and 78.67% increase respectively. The growth of iron-carbon nanotubes on the oxidized graphene / polypyrrole surface created the upper surface area of the carbon material. In addition, the synergistic effects of oxidized graphene and iron-carbon nanotubes have increased the load transfer efficiency, especially of the composite. The mobility of the polymer chains was limited by the strong ionic bonds of oxidized graphene sheets, WKF, and iron-carbon nanotubes in the polyester resin. This resulted in a very stiff compound with a crosslinked structure. Figure 12 (A) (B) shows tensile stress-strain curves, (B) shows iron-carbon nanotubes grown on WKF / PES, polypyrrole coated WKF / PES, oxidized graphene / polypyrrol coated WKF / PES, polypyrrole coated WKF / PES, Tensile strength and modulus of iron-carbon nanotubes grown on coated WKF / PES are shown. The in-plane stress deformation curve and the shear strength table are shown in Figs. 13 (A) and (B). The shear strength shown in Fig. 13 (B) was calculated as follows.
here,
(M), Fm is the maximum plane load (N), b is the specimen width (mm) and d is the specimen thickness (mm). Failures due to shear effects are mainly managed by micro-defects on the matrix. In each case, the slope of the curve is reduced by the damage in the composite that occurs when more pressure is applied. The ratio extension line was higher in coated WKF / PES and iron-carbon nanotube WKF / PES composites than in the WKF / PES composite. Polypyrrole and oxidized graphene / polypyrrole WKF / PES composites endured higher shear than the WKF / PES composites. The top surface area resulting from the π-π interaction between oxidized graphene and two polypyrrole bonds, the wrinkled, planar geometry of oxidized graphene, and the interaction between WKF and PES ultimately determined the physical properties of the composite. In addition, the oxygen-containing functional groups on the surface of the oxidized graphene sheets strongly interacted with WKF, polypyrrole and PES, creating a strong bond between them. Composites containing iron - carbon nanotubes grown on polypyrrole and oxidized graphene / polypyrrole coated WKF / PES increased in plane shear strength by 65.59% and 81.39%, respectively. The mechanical performance was greatly enhanced in WKF / PES composites containing iron-carbon nanotubes grown on oxidized graphene / polypyrrole-coated fibers. Oxide graphene / polypyrrole coatings Iron-carbon nanotubes synthesized on WKF can have very high top surfaces for interacting with PES and WKF thanks to the bonding of iron nanomolecules to their ends and the oxidation graphene nanosheets there was. Load transfer from the polymer matrix to the fibers was effectively accomplished through an active network structure with a high density of iron-carbon nanotubes grown on the WKF surface. 13 (A) is a planar shear reaction stress variation curve, and (B) is a WKF / PES. PPY Coated WKF / PES, Grafted Oxidized / Polypyrrole Coated WKF / PES, Coated WKF / PES Coated Iron-Carbon Nanotubes and Oxidized Grafted / Polypyrrole Coated WKF / PES Shear force.The impact resistance of the WKF composites is shown in Figure 14 (A) as an absorbed energy table as a function of time. The impact energy is the amount of kinetic energy transferred from the impact device to the composite. In the case of a low velocity impact, the sum of the absorbed energy and the rebound energy is the impact energy. Absorbed energy is the amount of energy dissipated in the composite immediately after the impact ends and consists of bending strain energy and exfoliation energy. Composites made through in situ polymerization of polypyrrole in WKF have a stronger impact resistance (19.49% increase) than the WKF / PES composite. The compounds also absorb more of the release energy due to interfacial interactions between oxidized graphene, WKF, polypyrrole, and PES. These increases in energy absorption include: 1) the interaction between the functional groups of oxidized graphene and the carboxylic acid and amine groups of WKF, 2) the interaction of polypyrrole with carboxylic acid groups of WKF, 3) 4) the enhanced surface area of the interaction assigned by the grafted oxide nanosheets, and 5) the interaction between the ester groups of the PES and the functional groups of the WKF do. Composites containing iron-carbon nanotubes grown on polypyrrole coated WKF / PES exhibited an increase in absorption energy by 77.29%. The iron nanomolecules enhanced the surface area of the interaction and the nanotubes formed a crosslinked structure with the matrix. The absorption energy was highest (84.03%) in composites containing iron-carbon nanotubes grown on oxidized graphene / polypyrrole coated WKF / PES. In these samples, the iron-carbon nanotubes bonded to the graphene oxide nanosheets can have a high specific surface which allows enhanced interaction at the interface. Previous studies have shown that the impact resistance of woven Kevlar fiber / epoxy composites has been enhanced after making carbon nanotubes with multiple walls. Here we show that the interaction between WKF, polypyrrole, oxidized graphene, iron-carbon nanotubes, and PES has created an extremely networked structure within the synthetic material.
Figure 14 (B) shows the velocity-time response curve in WKF composites. The penetration limit, i. E. The difference between the incidence rate and the residual rate, was the smallest in the man WKF / PES composite. The penetration limit was greatest in the samples containing iron-carbon nanotubes on oxidized graphene / polypyrrole coated WKF / PES. This is due to the stiffness created by nanotubes and oxidized graphene nanosheets. Other samples have reduced penetration limits in the following order: polypyrrole / oxidized graphene coating WKF / iron carbon nanotube on PES> polypyrrole coating WKF / iron carbon nanotube on PES> graphene oxide / polypyrrole coating WKF / PES> Polypyrrole Coating WKF / PES> Man WKF / PES. The decrease in the rate ratio, including the degree of enhancement of interactions within the composite, was higher in the iron-carbon nanotube samples. It can be seen that this resulted in a highly reinforced composite with excellent interfacial adhesion. 14 (A) (B) shows the energy-time response, (B) the iron-carbon nanotube grown in WKF / PES, polypyrrol coated WKF / PES, oxidized graphene / polypyrrol coated WKF / PES, polypyrrol coated WKF / PES, Time response curves of iron-carbon nanotubes grown in WKF / PES.
Figure 15 shows the electrical conduction of WKF composites. Electrically conductive polypyrrole was coated on non-conducting WKF to produce a WKF / PES composite with electrical conductivity. The iron-carbon nanotubes grown on the polypyrrole-coated WKF were joined together to further increase the electrical conductivity. Conductivity in the polypyrrole-coated Kevlar made of various concentrations of FeCl3 was 0.68 S / cm. The electrical conductivity of the polypyrrole coated WKF / PES composites in this study was 0.016 S / cm. Conductivity was reduced due to PES used in this study. Conductive polyaniline coated glass fiber / isotactic polypropylene / maleic anhydride conjugated polypropylene exhibited a conductivity of 1 X 10 -9 S / cm. Carbon nanotubes and their covalent iron nanomolecules may have been responsible for the electrical conductivity observed in the compositions of this study. It is believed that the iron carbide merging increases the electrical transport properties of polymer composites. Liu et al. Reported that polypyrrole-coated fly ash has an electrical conductivity of 0.87 S / cm while growing carbon nanotubes on its surface through microwave irradiation. However, the oxidized graphene / polypyrrole coated WKF / PES composites in this study have lower electrical conductivity than the polypyrrole coated WKF / PES, due to the oxygen-containing functional groups on the oxidized graphene nanosheets. These groups effectively blocked the current flow by acting as an electronic wall for WKF. The highest conductivity in this study was found in composites containing iron-carbon nanotubes grown on oxidized graphene / polypyrrole coated WKF / PES. FIG. 15 is a graph showing the results of an iron-carbon nanotube grown on a polypyrrole coated WKF / PES, a polypyrrole coated WKF / PES, an oxidized graphene / polypyrrole coated WKF / PES, and an oxidized graphene / polypyrrole coated WKF / This shows the electrical conduction of the tubes.
According to the above, a domestic microwave oven and a ferrocene catalyst were used to synthesize carbon nanotubes with layer nanomolecules on WKF surfaces coated with polypyrrole or oxidized graphene / polypyrrole. This technology is a fast, cost-effective way to overcome obstacles associated with CVD methods. By fixing the iron-carbon nanotubes on the fiber surface, aggregation and heterodispersity could also be prevented. Surface treatment of WKF produced carboxylic acid and amine functional groups that improved the bonding of oxidized graphene and polypyrrole. The composites were made of iron-carbon nanotubes grown on WKF using vacuum assisted resin transfer molding (VARTM). Raman spectroscopic analysis confirmed the formation of oxidized graphene and the growth of nanotubes on the Kevlar surface and demonstrated enhanced strength in D and G bands. SEM analysis confirmed that iron - carbon nanotubes were grown on polypyrrole and oxidized graphene / polypyrrole coated WKF surfaces with iron molecules at the ends of the nanotubes. Nanotube growth was highest at a substrate: ferrocene ratio of 1: 1 and decreased at lower ferrocene ratios. TEM analysis demonstrated that the nanotubes grew with iron nanomolecules at their ends or between them. WKF surface functionalization was characterized by FTIR analysis. Both FTIR and XRD analyzes confirmed the growth of iron-carbon nanotubes and showed intermolecular interactions between WKF, polypyrrole, oxidized graphene, carbon nanotubes, and PES. The tensile strength and modulus increased by 105.41% and 125.57%, respectively, in composites containing iron-carbon nanotubes grown on oxidized graphene / polypyrrole coated WKF / PES. Composites with iron - carbon nanotubes grown on polypyrrole coated WKF / PES increased by 78.67% and 89.82%, respectively, in the same variables. The in-plane shear strengthening was found to be 64.59% and 81.39% in the composite of iron-carbon nanotubes on polyketone coated WKF / PES and iron-carbon nanotubes on oxidized graphene / polypyrrol coated WKF / PES, respectively. The impact energy absorption was also increased to 84.03% and the penetration limit of the iron - carbon nanotube samples was larger than that of the master composite. Essentially electrically insulating WKF / PES composites have become electrically conductive by incorporating iron-carbon nanotubes. The interaction between WKF, polypyrrole, oxidized graphene, iron-carbon nanotubes, and PES matrix enhanced the physical and electrical performance of such WKF composites.
While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.
10,100 ...
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Claims (15)
Coating a mixture of polypyrrole (PPy) or polypyrrole with graphene oxide (GO) on the surface of the fiber material;
Immersing the fiber material in a catalytic metal aqueous solution; And
And irradiating the fiber material with microwaves to grow columnar carbon nanotubes on the surface of the fiber material.
The step of surface-treating the fiber material comprises:
A step of dipping the fibrous material in a basic aqueous solution so as to produce carboxylic acid groups, followed by a basic treatment, a step of drying the basic treated fibrous material after drying, and a step of acidifying the fibrous material by immersing the fibrous material in an acidic aqueous solution ≪ / RTI >
Wherein the basic treatment comprises:
Wherein the fiber material is immersed in an aqueous 10% sodium hydroxide solution at room temperature for 20 minutes to 1 hour.
The acid treatment may comprise:
Wherein the fiber material is immersed in an aqueous hydrochloric acid solution for 5 seconds to 15 seconds.
Wherein the catalyst metal aqueous solution is an FeCl 3 aqueous solution.
Stacking a plurality of the fiber materials so as to be spaced apart from each other; And
And filling fibers between the fibrous materials to bind the fibrous materials.
The step of forming the carbon nanotubes on the surface of the fiber material comprises:
Surface treating the fiber material to produce carboxylic acid groups on the surface of the fiber material;
Coating a mixture of polypyrrole (PPy) or polypyrrole with graphene oxide (GO) on the surface of the fiber material;
Immersing the fiber material in an aqueous catalytic metal solution;
And irradiating the fiber material with microwaves to grow columnar carbon nanotubes on the surface of the fiber material.
The step of surface-treating the fiber material comprises:
Immersing the fiber material in a basic aqueous solution to perform a basic treatment;
Drying the basic-treated fiber material after drying,
And immersing the fiber material in an acidic aqueous solution to perform an acid treatment.
Wherein the basic treatment comprises:
Wherein the fiber material is immersed in an aqueous 10% sodium hydroxide solution at room temperature for 20 minutes to 1 hour.
The acid treatment may comprise:
Wherein the fiber material is immersed in an aqueous hydrochloric acid solution for 5 seconds to 15 seconds.
The catalyst metal aqueous solution may contain,
FeCl 3 aqueous solution.
The step of growing the columnar carbon nanotubes on the surface of the fiber material comprises:
Wherein the carbon nanotubes are formed on the upper and lower surfaces of the fiber material so that the carbon nanotubes face each other or are staggered and the side surfaces overlap each other between the laminated fiber materials.
Columnar carbon nanotubes formed on the upper and lower surfaces of the fiber material and arranged to face each other in the space; And
And a resin layer filled in the space to bond the fiber materials so that the carbon nanotubes are impregnated.
The carbon nanotubes
Wherein the plurality of fibers are disposed so as to face each other and are alternately arranged in the space.
The carbon nanotubes may include,
A composite fiber body formed by coating a mixture of polypyrrole (PPy) or polypyrrole with graphene oxide (GO) on the surface of the fiber material, followed by irradiation of microwaves.
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