WO2019208997A1 - Fibres composites comprenant des fibres de graphène sur lesquelles est formé un film de revêtement et procédé de préparation de ces fibres - Google Patents

Fibres composites comprenant des fibres de graphène sur lesquelles est formé un film de revêtement et procédé de préparation de ces fibres Download PDF

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WO2019208997A1
WO2019208997A1 PCT/KR2019/004865 KR2019004865W WO2019208997A1 WO 2019208997 A1 WO2019208997 A1 WO 2019208997A1 KR 2019004865 W KR2019004865 W KR 2019004865W WO 2019208997 A1 WO2019208997 A1 WO 2019208997A1
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graphene
composite fiber
coating solution
fibers
fiber
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PCT/KR2019/004865
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English (en)
Korean (ko)
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한태희
성태현
엄원식
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한양대학교 산학협력단
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Priority claimed from KR1020190045910A external-priority patent/KR102711578B1/ko
Application filed by 한양대학교 산학협력단 filed Critical 한양대학교 산학협력단
Publication of WO2019208997A1 publication Critical patent/WO2019208997A1/fr

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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
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
    • D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol

Definitions

  • the present invention relates to a composite fiber comprising a graphene fiber formed with a coating film and a method of manufacturing the same.
  • Graphene is the most excellent material among the existing materials with various characteristics such as strength, thermal conductivity and electron mobility. Accordingly, it is applied to various fields such as display, secondary battery, solar cell, automobile, and lighting, and is recognized as a strategic core material that will lead the growth of related industries, and technology for commercializing graphene has received much attention.
  • Korean Patent Publication No. 10-2013-0116598 (Application No .: 10-2012-0039129, Applicant: Korea Electronics and Telecommunications Research Institute), preparing a support fiber, preparing a graphene oxide containing solution, the Disclosed is a graphene fiber manufacturing method comprising coating a support fiber with the graphene oxide-containing solution to prepare a graphene oxide composite fiber, and separating the support fiber from the composite fiber.
  • One technical problem to be solved by the present invention is to provide a composite fiber including a graphene fiber formed with a coating film is improved uniformity of the polymer coating film and a method of manufacturing the same.
  • Another technical problem to be solved by the present invention is to provide a composite fiber with improved mechanical properties, including a graphene fiber with a coating film and a method for producing the same.
  • Another technical problem to be solved by the present invention is to provide a composite fiber including a graphene fiber formed with a coating film that can be manufactured by a simple process and a method of manufacturing the same.
  • the technical problem to be solved by the present invention is not limited to the above.
  • the present invention provides a method for producing a composite fiber.
  • the method for producing a composite fiber a step of preparing a coating solution having a controlled viscosity (viscosity) by mixing a polymer with a solvent, and providing the coating solution to graphene fibers, the graphene fibers Comprising the step of preparing a composite fiber formed with a coating film containing the polymer on the, wherein the composite fiber may include controlling the uniformity of the coating film according to the molecular weight of the polymer or the viscosity of the coating solution.
  • the molecular weight of the polymer may include less than 40500.
  • the viscosity of the coating solution may include more than 158.2 m Pas and less than 495.5 m Pas.
  • the method for producing a composite fiber when the viscosity of the coating solution is 158.2 m Pas or less mechanical properties of the composite fiber, when the viscosity of the coating solution is 495.5 m Pas or more the composite fiber It may include that the uniformity of the coating film to include.
  • preparing the coating solution may include preparing the polymer, and mixing the polymer with the solvent including water.
  • the step of preparing the composite fiber provided by the method of immersing the graphene fibers in the coating solution, according to the time that the graphene fibers are immersed in the coating solution, uniformity of the coating film And control the properties and mechanical properties of the composite fiber.
  • the time that the graphene fibers are immersed in the coating solution may include less than 10 seconds.
  • the uniformity of the coating film and the mechanical properties of the composite fiber May be controlled.
  • the number of times the graphene fibers are immersed in the coating solution may include two.
  • the present invention provides a composite fiber.
  • the composite fiber is a graphene fiber comprising a plurality of graphene sheet structure in which a plurality of graphene sheets sequentially stacked in the thickness direction, spaced apart from each other and extending in one direction, and the graphene
  • the fiber may be conformally wrapped, and may include a coating film containing a polymer.
  • the polymer may include polyvinyl alcohol (PVA).
  • PVA polyvinyl alcohol
  • the molecular weight of the polymer may include less than 40500.
  • Method for producing a composite fiber according to an embodiment of the present invention by mixing a polymer with a solvent to prepare a coating solution controlled viscosity, and providing the coating solution to graphene fibers, the graphene fibers on the Comprising a step of producing a composite fiber formed with the coating film comprising a polymer, the composite fiber may be controlled uniformity of the coating film according to the molecular weight of the polymer or the viscosity of the coating solution. Accordingly, the composite fiber with improved mechanical properties can be produced in a simple process.
  • FIG. 1 is a flowchart illustrating a method of manufacturing a composite fiber according to an embodiment of the present invention.
  • FIG. 2 is a view showing a manufacturing process of a composite fiber according to an embodiment of the present invention.
  • FIG 3 is a view showing a composite fiber according to an embodiment of the present invention.
  • Figure 4 is a flow chart illustrating the step of preparing a graphene fiber in the method for producing a composite fiber according to an embodiment of the present invention.
  • FIG. 5 is a view showing a manufacturing process of graphene fibers included in the composite fiber according to an embodiment of the present invention.
  • Figure 6 is a photograph taken by comparing the composite fibers prepared with a coating solution having a different viscosity.
  • Figure 7 is a photograph taken by comparing the composite fibers prepared with a coating solution containing different solvents.
  • FIG. 10 is a photograph comparing and photographing the composite fibers prepared by varying the number of times the graphene fibers are immersed in the coating solution.
  • 11 to 13 are graphs comparing the mechanical properties according to the molecular weight of the polymer included in the composite fiber according to an embodiment of the present invention.
  • 14 to 16 are graphs comparing the mechanical properties of composite fibers prepared from coating solutions having different viscosities.
  • 17 to 19 is a graph comparing the mechanical properties of the composite fibers prepared with a coating solution containing different solvents.
  • 20 to 22 is a graph comparing the mechanical properties of the composite fibers prepared by varying the time the graphene fibers are immersed in the coating solution.
  • 23 to 25 is a graph comparing the mechanical properties of the composite fibers prepared by varying the number of times the graphene fibers are immersed in the coating solution.
  • FIG. 26 is a graph showing the characteristic change that appears when coating the graphene fiber, including graphene oxide.
  • FIG. 27 is a graph comparing mechanical properties of composite fibers according to types of graphene included in graphene fibers and types of polymers included in a coating solution.
  • 29 is a photograph comparing the characteristics according to the molecular weight of the polymer included in the coating solution used in the manufacturing process of the composite fiber according to an embodiment of the present invention.
  • FIG. 30 is a graph comparing the characteristics according to the molecular weight of the polymer included in the coating solution used in the manufacturing process of the composite fiber according to an embodiment of the present invention.
  • first, second, and third are used to describe various components, but these components should not be limited by these terms. These terms are only used to distinguish one component from another. Thus, what is referred to as a first component in one embodiment may be referred to as a second component in another embodiment.
  • first component in one embodiment may be referred to as a second component in another embodiment.
  • second component in another embodiment.
  • Each embodiment described and illustrated herein also includes its complementary embodiment.
  • the term 'and / or' is used herein to include at least one of the components listed before and after.
  • connection is used herein to mean both indirectly connecting a plurality of components, and directly connecting.
  • the graphene fibers may include at least one of graphene oxide, reduced graphene oxide, and graphene.
  • FIG. 1 is a flowchart illustrating a method of manufacturing a composite fiber according to an embodiment of the present invention
  • Figure 2 is a view showing a manufacturing process of a composite fiber according to an embodiment of the present invention
  • Figure 3 is an embodiment of the present invention It is a figure which shows the composite fiber which followed.
  • the coating solution 10 may be prepared (S100).
  • preparing the coating solution 10 may include preparing a polymer, and mixing the polymer with a solvent. That is, the coating solution 10 may be prepared by mixing the polymer and the solvent.
  • the polymer may be at least one of polyvinyl alcohol (PVA) or polyvinyl chloride (PVC).
  • the solvent may be a material having a relatively slow volatilization rate compared to the alcohol.
  • the solvent may be water (H 2 O).
  • the solvent contains a material having a high volatilization rate, the coating solution 10 may be rapidly volatilized in the manufacturing process of the coating film 10 to be described later, thereby decreasing the uniformity of the coating film 10.
  • the coating solution 10 is provided to the graphene fiber 20, the composite fiber 30 can be produced (S200). According to an embodiment, the composite fiber 30 may be provided and manufactured by a method of dipping the graphene fiber 20 into the coating solution 10.
  • the manufacturing of the composite fiber 30 may include preparing the coating solution 10 and the graphene fiber 20, and immersing the graphene fiber 20 in the coating solution 10. It may include the step of.
  • the graphene fiber 20 may include graphene oxide.
  • the polymer may include PVA. That is, the composite fiber 30 may be formed by coating PVA on the graphene fiber 20 including graphene oxide.
  • the graphene fiber 20 may include reduced graphene oxide.
  • the polymer may include PVC. That is, the composite fiber 30 may be formed by coating PVC on the graphene fiber including the reduced graphene oxide.
  • the graphene fiber 20 containing graphene oxide is coated with PVA, and the graphene fiber 20 containing reduced graphene oxide is coated with PVC to thereby form the composite fiber 30.
  • Mechanical properties can be improved.
  • the type of the polymer according to the type of graphene included in the graphene fiber 20 is not limited.
  • the graphene fiber when the graphene fiber includes the reduced graphene oxide, the graphene fiber may be prepared by a method of joule heating the graphene oxide fiber.
  • the step of preparing the graphene fiber will be described with reference to FIG. 4.
  • Figure 4 is a flow chart illustrating the steps of preparing a graphene fiber in the method for producing a composite fiber according to an embodiment of the present invention
  • Figure 5 is a manufacturing process of the graphene fiber included in the composite fiber according to an embodiment of the present invention It is a figure which shows.
  • the source solution 50 may be prepared (S10).
  • the source solution 50 may include graphene oxide.
  • the source solution may be prepared by adding the graphene oxide to a solvent.
  • the solvent may be water or an organic solvent.
  • the organic solvent may be dimethyl sulfoxide (DMSO), ethylene glycol, ethylene glycol, N-methyl-2-pyrrolidone (NMP), dimethylformamide ( dimethylformamide, DMF).
  • the source solution 50 may be prepared by adding the graphene oxide to the organic solvent at a concentration of 5 mg / mL.
  • the source solution 50 is spun in the coagulation solution 60 may be prepared graphene oxide fiber 70 (S20).
  • the coagulation solution 60 may include a coagulant.
  • the graphene oxide fiber 70 manufactured by spinning the source solution 50 in the coagulation solution 60 may be coagulated by the coagulant included in the coagulation solution 60.
  • the coagulant calcium chloride (CaCl2), potassium hydroxide (KOH), sodium hydroxide (NaOH), sodium chloride (NaCl), copper sulfate (CuSO4), cetyltrimethylammonium bromide (CTAB), or It may be any one of chitosan.
  • the source solution 50 contained in the source container 100 through the spinneret 120 connected to the source container 100, the coagulation solution 60 This may be radiated into the coagulation bath 150.
  • the graphene oxide fiber 70 may be separated from the coagulation solution 60, washed, and dried.
  • the graphene oxide fiber 70 may be separated from the coagulation bath 150 containing the coagulation solution 60 by a guide roller 170 and may come out to the outside.
  • the graphene oxide fiber 70 separated from the coagulation solution 60 may include the coagulant.
  • the washing solution used in the washing process may be an alcoholic aqueous solution.
  • moisture contained in the graphene oxide fiber 70 may be naturally dried in the air.
  • the graphene oxide fiber 70 naturally dried in air may be secondaryly dried. That is, at least a portion of the water remaining in the graphene oxide fiber 70 may be removed through the heating process.
  • both ends of the graphene oxide fiber 70 may be fixed.
  • length shrinkage of the graphene oxide fiber 70 may be minimized. That is, when the graphene oxide fiber 70 is dried, the graphene oxide fiber 70 may be shrunk in length. Accordingly, when both ends of the graphene oxide fiber 70 are fixed, the length shrinkage of the graphene oxide fiber 70 may be minimized.
  • the graphene fibers to be described later are manufactured using the graphene oxide fiber 70 minimized in length shrinkage, mechanical strength of the graphene fibers may be improved.
  • the graphene oxide fiber 70 may be wound and dried at the same time through the heating process. As shown in FIG. 5, after the cleaning process is finished, the graphene oxide fiber 70 may be wound by a winding roller 190 while the drying process is performed.
  • the manufacturing of the base fiber may include preparing a reducing solution including a reducing agent, and immersing the graphene oxide fibers in the reducing solution.
  • the reducing agent may be Hydroiodic acid (HI).
  • the reducing solution may be a solution in which HI having a concentration of 50 wt% and water having a concentration of 50 wt% are mixed.
  • the graphene oxide fiber is reduced, the base fiber can be produced.
  • the base fiber is joule heated (joule heating), the graphene fiber can be produced (S40). That is, the graphene fiber may be manufactured by applying a current to the base fiber.
  • the composite fiber 30 may include a coating film 10 that conformally surrounds the graphene fiber 10 and the graphene fiber 20.
  • the graphene fiber 10 may include a graphene sheet structure in which a plurality of graphene sheets are sequentially stacked in a thickness direction.
  • the graphene fiber 10 may be a plurality of graphene sheet structure, it is spaced apart from each other and extend in one direction.
  • the coating film 10 may be formed by hardening the coating solution 10. Accordingly, the coating film 10 may include the polymer.
  • the uniformity of the coating film 10 may be controlled according to the molecular weight of the polymer or the viscosity of the coating solution 10.
  • mechanical properties of the composite fiber 30 may be controlled according to the molecular weight of the polymer or the viscosity of the coating solution 10.
  • the method of manufacturing the composite fiber according to the embodiment by controlling the molecular weight of the polymer or the viscosity of the coating solution 10, it is possible to uniformly manufacture the coating film (10).
  • the molecular weight of the polymer or the viscosity of the coating solution 10 it is possible to improve the mechanical properties of the composite fiber (30).
  • the mechanical properties of the composite fiber 30 may be tensile strength, elongation, modulus, and the like.
  • a specific method of controlling the uniformity of the coating film 10 and the mechanical properties of the composite fiber is controlled by controlling the molecular weight of the polymer or the viscosity of the coating solution 10.
  • the viscosity of the coating solution 10 may be controlled according to the concentration of the polymer in the coating solution 10. Specifically, as the concentration of the polymer in the coating solution 10 increases, the viscosity of the coating solution 10 may increase.
  • the viscosity of the coating solution 10 may be greater than 158.2 m Pas and less than 495.5 m Pas.
  • the concentration of the polymer in the coating solution may be greater than 65 mg / ml less than 85 mg / ml.
  • the uniformity of the coating film 10 can be improved. Accordingly, the mechanical properties of the composite fiber 30 can be improved. On the contrary, when the viscosity of the coating solution 10 is 158.2 m Pas or less, a problem may occur in that mechanical properties of the composite fiber 30 are lowered. In addition, when the viscosity of the coating solution 10 is 495.5 m Pas or more, a problem may occur in that the uniformity of the coating film 10 included in the composite fiber 30 is lowered.
  • the mechanical properties of the composite fiber can be controlled according to the molecular weight of the polymer. Specifically, when the molecular weight of the polymer is less than 40500 or more than 166000, the mechanical properties (eg, tensile strength, elongation, etc.) of the composite fiber can be improved.
  • the coating solution 10 is to increase the viscosity increase in accordance with the concentration of the polymer.
  • the coating solution 10 is prepared using a polymer having a relatively high molecular weight (eg, 166000 or more)
  • the coating solution having a viscosity in the range of more than 158.2 m Pas and less than 495.5 m Pas as described above ( 10) may not be easy to manufacture.
  • the mechanical properties (eg, tensile strength, elongation, etc.) of the composite fiber is improved, and the convenience of the composite fiber manufacturing process can be improved. have.
  • the composite fiber 30 when the composite fiber 30 is manufactured by immersing the graphene fiber 20 in the coating solution 10, the graphene fibers 20 in the coating solution 10 As the time is immersed, the uniformity of the coating layer 10 and the mechanical properties of the composite fiber 30 can be controlled.
  • the time for which the graphene fiber 20 is immersed in the coating solution 10 may be 10 seconds.
  • the graphene fiber 20 is immersed in the coating solution 10 for 10 seconds or more, cracks are generated in the coating film 10, thereby decreasing uniformity of the coating film 10. Can be.
  • mechanical properties of the composite fiber 30 may be degraded.
  • the composite fiber 30 when the composite fiber 30 is manufactured by immersing the graphene fiber 20 in the coating solution 10, the graphene fiber 20 in the coating solution 10 According to the number of times the immersion, the uniformity of the coating film 10 and the mechanical properties of the composite fiber 30 can be controlled.
  • the number of times the graphene fiber 20 is immersed in the coating solution 10 may be two times.
  • the number of times the graphene fiber 20 is immersed in the coating solution 10 is more than two times, cracks are generated in the coating film 100 so that the uniformity of the coating film 10 is increased.
  • mechanical properties of the composite fiber 30 may be degraded.
  • Method for producing a composite fiber by mixing the polymer with a solvent to prepare the coating solution 10 is controlled viscosity, and the coating solution 10 to the graphene fibers 20 ), To prepare the composite fiber 30 in which the coating film 10 including the polymer on the graphene fiber 20 is formed, wherein the composite fiber 30 of the polymer
  • the uniformity of the coating film 10 may be controlled according to the molecular weight or the viscosity of the coating solution 10. Accordingly, the composite fiber with improved mechanical properties can be produced in a simple process.
  • Figure 6 is a photograph taken by comparing the composite fibers prepared with a coating solution having a different viscosity.
  • FIG. 6 (a) normal graphene fibers (GF) are shown in FIG. 6 (a) by scanning electron microscope (SEM) scanning, and graphene fibers are coated in a coating solution. SEM images of the composite fibers prepared by dipping were shown in FIGS. 6B and 6C.
  • the coating solution for preparing the composite fiber shown in Figure 6 (b) was prepared to exceed the concentration of 75 mg / ml and the viscosity of 460 m Pas by mixing water (H 2 O) and PVA
  • the coating solution for producing the composite fiber shown in 6 (c) was prepared by mixing water (H 2 O) and PVA to a concentration of 75 mg / ml and a viscosity of 460 m Pas or less.
  • the composite fiber is a PVA coating film formed on the graphene fibers compared to the normal graphene fibers.
  • the viscosity of the coating solution used in the process of producing the composite fiber exceeds 460 m Pas, it was confirmed that the cracking point (CP) was formed on the coating film. Therefore, when manufacturing the composite fiber according to the embodiment of the present invention, it can be seen that controlling the viscosity of the coating solution to 460 m Pas or less, a method of improving the uniformity of the coating film.
  • Figure 7 is a photograph taken by comparing the composite fibers prepared with a coating solution containing different solvents.
  • FIG. 7 (a) SEM photographs of general graphene fibers (GF) are shown in FIG. 7 (a), and composites prepared by dipping graphene fibers in a coating solution. SEM images of the fibers are shown in FIGS. 7B and 7C.
  • the coating solution for preparing the composite fiber shown in Figure 7 (b) was prepared by mixing water (H 2 O) and PVA
  • the coating for producing the composite fiber shown in Figure 7 (c) The solution was prepared by mixing PVA again in a solution in which water (H 2 O) and ethanol (EtOH) were mixed at a ratio of 1: 1.
  • FIGS. 8B and 8C the SEM graph of the normal graphene fibers (graphene fiber, GF) is shown in Figure 8 (a), a composite prepared by providing a coating solution to the graphene fibers SEM images of the fibers are shown in FIGS. 8B and 8C.
  • the composite fiber shown in (b) of FIG. 8 was manufactured by painting a coating solution on the graphene fibers, and the composite fiber shown in (c) of FIG. 8 contained graphene fibers in the coating solution. It was prepared by dipping.
  • the coating film of the composite fiber according to Figure 8 (c) is compared with the coating film of the composite fiber according to Figure 8 (b), it can be seen that the uniformity is improved. there was. Therefore, when manufacturing the composite fiber according to the embodiment of the present invention, it can be seen that using the method of immersing the graphene fibers in the coating solution, a method of improving the uniformity of the coating film.
  • normal graphene oxide fibers are SEM photographed as shown in FIG. 9 (a), and prepared by immersing graphene fibers in a coating solution. SEM images of the composite fibers were shown in FIGS. 9B to 9D. However, the composite fiber shown in (b) of FIG. 9 was prepared by immersing graphene fibers in the coating solution for 1 second, and the composite fiber shown in (c) of FIG. It was prepared by soaking for 10 seconds, and the composite fiber shown in (d) of FIG. 8 was prepared by soaking graphene fibers in the coating solution for 30 seconds.
  • the coating film of the composite fiber according to Figure 9 (b) is uniform, compared to the coating film of the composite fiber according to Figures 9 (c) and (d) The improvement was confirmed.
  • the coating film of the composite fiber according to (d) of FIG. 9 was compared with the coating film of the composite fiber of (b) and (c) of Figure 9, it was confirmed that a large number of cracks (crack) was formed. Therefore, when manufacturing the composite fiber according to an embodiment of the present invention, it can be seen that controlling the time to immerse the graphene fibers in the coating solution to less than 10 seconds, a method of improving the uniformity of the coating film.
  • FIG. 10 is a photograph comparing and photographing the composite fibers prepared by varying the number of times the graphene fibers are immersed in the coating solution.
  • FIG. 10 (a) SEM photographs of general graphene oxide fibers (GOF) are shown in FIG. 10 (a), and prepared by immersing graphene fibers in a coating solution. SEM images of the obtained composite fibers are shown in FIGS. 10B to 10D.
  • the composite fiber shown in (b) of FIG. 10 is prepared by immersing graphene fibers in the coating solution once, and the composite fiber shown in FIG. 10 (c) has twice the graphene fibers in the coating solution. It was prepared by dipping, and the composite fiber shown in (d) of FIG. 10 was prepared by immersing graphene fibers three times in a coating solution.
  • the coating film of the composite fiber according to (c) of FIG. 10 has a uniformity as compared to the coating film of the composite fiber of (b) and (d) of FIG. The improvement was confirmed.
  • the coating film of the composite fiber according to (d) of FIG. 10 was compared with the coating film of the composite fiber according to (b) and (c) of FIG. 10, and it was confirmed that a large number of cracks were formed. Therefore, when manufacturing the composite fiber according to the embodiment of the present invention, it can be seen that controlling the number of times the immersion of graphene fibers in the coating solution twice, a method of improving the uniformity of the coating film.
  • 11 to 13 are graphs comparing the mechanical properties according to the molecular weight of the polymer included in the composite fiber according to an embodiment of the present invention.
  • the composite fiber according to the embodiment including a graphene oxide fiber (GOF), and polymers having different molecular weights (18000, 40500, 72500, 104500, 166000) Ready Then, the tensile strength (MPa), elongation at break (%), and modulus (GPa) of the graphene oxide fibers and the composite fibers were measured and shown in FIGS. 11 to 13, respectively. .
  • GAF graphene oxide fiber
  • the composite fiber containing a polymer having a molecular weight of 18000 significantly increased the tensile strength.
  • the composite fiber containing the polymer having a molecular weight of 40500 was confirmed that the tensile strength is lower than that of the composite fiber containing the polymer having a molecular weight of 18000.
  • the composite fiber containing a polymer having a molecular weight of 166000 or more also exhibits high tensile strength.
  • the composite fiber containing a polymer having a molecular weight of 18000 significantly increased the elongation.
  • the composite fiber containing the polymer having a molecular weight of 40500 was confirmed that the elongation rate is lower than that of the composite fiber containing a polymer having a molecular weight of 18000.
  • the composite fiber containing a polymer having a molecular weight of 166000 or more also exhibits high elongation.
  • the normal graphene oxide fiber, a composite fiber comprising a polymer having a molecular weight of 18000, and a composite fiber comprising a polymer having a molecular weight of 40500 exhibits an elastic force of about 55 GPa, a molecular weight of 72500 It was confirmed that the composite fiber including the polymer having an elastic force of about 48 GPa, the composite fiber including the polymer having a molecular weight of 104500, and the composite fiber including the polymer having a molecular weight of 166000 showed an elastic force of about 50 GPa.
  • the composite fiber including the polymer having an elastic force of about 48 GPa, the composite fiber including the polymer having a molecular weight of 104500, and the composite fiber including the polymer having a molecular weight of 166000 showed an elastic force of about 50 GPa.
  • 14 to 16 are graphs comparing the mechanical properties of composite fibers prepared from coating solutions having different viscosities.
  • the normal graphene oxide fibers exhibit a tensile strength of about 220 MPa
  • composite fibers made of a coating solution (concentration 45 mg / ml) having a viscosity of 52.5 m Pas has a tensile strength of about 230 MPa
  • Composite fibers made with a coating solution having a viscosity of 120.8 m Pas (concentration 55 mg / ml) exhibit a tensile strength of about 228 MPa and made with a coating solution with a viscosity of 158.2 m Pas (concentration 65 mg / ml).
  • Composite fibers exhibit a tensile strength of about 250 MPa
  • composite fibers prepared with a coating solution having a viscosity of 460 m Pas exhibit a tensile strength of about 280 MPa and a coating having a viscosity of 495.5 m Pas. It was confirmed that the composite fiber prepared as a solution (concentration 85 mg / ml) showed a tensile strength of about 200 MPa. That is, it can be seen that the tensile strength of the composite fiber prepared with a coating solution (concentration 75 mg / ml) having a viscosity of 460 m Pas is the highest.
  • the normal graphene oxide fiber shows an elongation of about 0.8%
  • the composite fiber prepared with a coating solution (concentration 45 mg / ml) having a viscosity of 52.5 m Pas shows an elongation of about 0.7%
  • Composite fibers made with a coating solution having a viscosity of 120.8 m Pas (concentration 55 mg / ml) exhibited an elongation of about 0.8% and made with a coating solution having a viscosity of 158.2 m Pas (concentration 65 mg / ml)
  • Composite fibers exhibit an elongation of about 0.9%
  • composite fibers prepared with a coating solution with a viscosity of 460 m Pas exhibit an elongation of about 0.7%
  • a coating solution with a viscosity of 495.5 m Pas It was confirmed that the composite fiber prepared at (concentration 85 mg / ml) showed an elongation of about 0.6%.
  • the normal graphene oxide fibers exhibit an elastic force of about 30 GPa
  • the composite fiber made of a coating solution (concentration 45 mg / ml) having a viscosity of 52.5 m Pas exhibits an elastic force of about 38 GPa
  • Composite fibers prepared with a coating solution having a viscosity of 120.8 m Pas (concentration 55 mg / ml) exhibit an elastic force of about 25 GPa
  • a coating solution having a viscosity of 158.2 m Pas Concentration 65 mg / ml
  • Composite fibers exhibit an elastic force of about 32 GPa and composite fibers made with a coating solution (concentration 75 mg / ml) with a viscosity of 460 m Pas exhibit an elastic force of about 42 GPa and a coating solution with a viscosity of 495.5 m Pas. It was confirmed that the composite fiber prepared at (concentration 85 mg / ml) exhibited an elastic force of about 37 GPa
  • 17 to 19 is a graph comparing the mechanical properties of the composite fibers prepared with a coating solution containing different solvents.
  • GF general graphene fibers
  • composite fibers made of a coating solution using water (H 2 O) as a solvent, and water (H 2 O) and ethanol (EtOH) )
  • MPa tensile strength
  • elongation at break %
  • GPa modulus
  • 20 to 22 is a graph comparing the mechanical properties of the composite fibers prepared by varying the time the graphene fibers are immersed in the coating solution.
  • composite graphene oxide fibers (GOF) and graphene fibers are immersed in a coating solution for 1 second for a composite fiber, and graphene fibers are prepared for 10 seconds in a coating solution.
  • Composite fibers prepared by dipping and graphene fibers were immersed in the coating solution for 30 seconds for tensile fibers (MPa), elongation at break (%), and modulus for each of the composite fibers prepared. , GPa) were measured and shown in FIGS. 20 to 22, respectively.
  • the normal graphene oxide fiber exhibits a tensile strength of about 190 MPa
  • the composite fiber prepared by immersing the graphene fiber in the coating solution for 1 second has a tensile strength of about 290 MPa.
  • Composite fibers produced by fin fibers immersed in the coating solution for 10 seconds showed a tensile strength of about 220 MPa
  • the normal graphene oxide fiber exhibits a tensile strength of about 0.35%
  • the composite fiber prepared by immersing the graphene fiber in the coating solution for 1 second time exhibits a tensile strength of about 0.6%
  • Composite fibers produced by fin fibers immersed in a coating solution for 10 seconds showed a tensile strength of about 0.58%
  • composite fibers produced by graphene fibers immersed in a coating solution for 30 seconds had a tensile strength of about 0.58%. It could be confirmed that it represents. That is, it was confirmed that the graphene fibers were immersed in the coating solution for 1 second for the highest tensile strength of the prepared composite fiber.
  • the normal graphene oxide fiber exhibits an elastic force of about 53 GPa
  • the composite fiber prepared by immersing the graphene fiber in the coating solution for 1 second time exhibits an elastic force of about 50 GPa
  • graphene fiber The composite fiber prepared by dipping for 10 seconds in the coating solution exhibited an elastic force of about 42 GPa
  • the composite fiber prepared by soaking graphene fiber for 30 seconds in the coating solution showed an elastic force of about 40 GPa.
  • 23 to 25 is a graph comparing the mechanical properties of the composite fibers prepared by varying the number of times the graphene fibers are immersed in the coating solution.
  • GAF general graphene oxide fibers
  • composite fibers prepared by immersing graphene fibers once in a coating solution and graphene fibers prepared by immersing twice in a coating solution
  • Tensile strength (MPa), elongation at break (%), and modulus (GPa) were measured for each of the composite fibers and the composite fibers prepared by immersing the graphene fibers three times in the coating solution. 23 to 25, respectively.
  • the normal graphene oxide shows a tensile strength of about 210 MPa
  • composite fibers prepared by immersing graphene fibers in the coating solution once shows a tensile strength of about 260 MPa
  • the composite fiber prepared by immersing twice in the coating solution exhibited a tensile strength of about 270 MPa
  • the composite fiber prepared by immersing the graphene fiber three times in the coating solution exhibited a tensile strength of about 200 MPa.
  • the normal graphene oxide shows an elongation of about 0.79%
  • the graphene fibers coated The composite fiber prepared by immersing twice in a solution exhibited an elongation of about 0.81
  • the composite fiber prepared by immersing graphene fibers three times in a coating solution exhibited an elongation of about 0.73%.
  • the normal graphene oxide exhibits an elastic force of about 30 GPa
  • FIG. 26 is a graph showing the characteristic change that appears when coating the graphene fiber, including graphene oxide.
  • graphene fibers including graphene oxide, and composite fibers (PVA coated GOF) according to the embodiment prepared by coating PVA on the graphene fibers described above, respectively, for each Stress (N) according to strain (%) was measured and shown.
  • FIG. 27 is a graph comparing mechanical properties of composite fibers according to types of graphene included in graphene fibers and types of polymers included in a coating solution.
  • the composite fibers prepared by coating the PVC are compared with the composite fibers prepared by coating the PVA. It can be seen that it exhibits high mechanical properties.
  • the source solution containing graphene oxide was spun into a coagulation solution to prepare preliminary graphene fibers, and then dried to prepare graphene fibers.
  • PVA is coated in each case in which both ends of the preliminary graphene fibers are fixed to limit the contraction (Fixed GOF) and not the contraction (Not fixed GOF).
  • MPa Tensile strength
  • Elongation %.
  • 29 is a photograph comparing the characteristics according to the molecular weight of the polymer included in the coating solution used in the manufacturing process of the composite fiber according to an embodiment of the present invention.
  • the graphene fibers (Before coated) before the PVA coating composite fiber prepared by coating a PVA having a molecular weight of 18K, PVA having a molecular weight of 40.5K
  • the composite fiber prepared by coating, the composite fiber prepared by coating a PVA having a molecular weight of 104.5K, and the composite fiber prepared by coating a PVA having a molecular weight of 166K were shown by SEM photographing.
  • FIG. 30 is a graph comparing the characteristics according to the molecular weight of the polymer included in the coating solution used in the manufacturing process of the composite fiber according to an embodiment of the present invention.
  • the composite fiber according to the embodiment of the present application may be utilized in various industrial fields, such as a power transport ship, a motor, a vehicle interior.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

L'invention concerne un procédé de préparation de fibres composites. Ce procédé de préparation de fibres composites peut comprendre les étapes consistant à : mélanger un polymère et un solvant pour préparer une solution de revêtement ; et appliquer la solution de revêtement sur des fibres de graphène pour préparer des fibres composites, l'uniformité du film de revêtement dans les fibres composites pouvant être régulée en fonction du poids moléculaire du polymère ou de la viscosité de la solution de revêtement.
PCT/KR2019/004865 2018-04-26 2019-04-23 Fibres composites comprenant des fibres de graphène sur lesquelles est formé un film de revêtement et procédé de préparation de ces fibres WO2019208997A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2018-0048308 2018-04-26
KR20180048308 2018-04-26
KR1020190045910A KR102711578B1 (ko) 2018-04-26 2019-04-19 코팅막이 형성된 그래핀 섬유를 포함하는 복합 섬유 및 그 제조 방법
KR10-2019-0045910 2019-04-19

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Citations (6)

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Publication number Priority date Publication date Assignee Title
KR20090072480A (ko) * 2007-12-28 2009-07-02 주식회사 효성 파라형 아라미드 섬유의 제조방법
KR20120105179A (ko) * 2011-03-15 2012-09-25 한양대학교 산학협력단 그라핀 복합 섬유 및 이의 제조 방법
KR20120107026A (ko) * 2011-03-15 2012-09-28 한양대학교 산학협력단 그라핀 섬유 및 이의 제조 방법
KR20140105442A (ko) * 2011-10-27 2014-09-01 갈모어, 인코포레이티드 복합체 그래핀 구조
JP2016531824A (ja) * 2014-04-28 2016-10-13 寧波墨西科技有限公司Ｎｉｎｇｂｏ Ｍｏｒｓｈ Ｔｅｃｈｎｏｌｏｇｙ ＣＯ．， ＬＴＤ． グラフェン複合粉体材料及びその製造方法
KR20180039329A (ko) * 2016-10-10 2018-04-18 한양대학교 산학협력단 그래핀/고분자 복합 섬유 및 이의 제조방법

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090072480A (ko) * 2007-12-28 2009-07-02 주식회사 효성 파라형 아라미드 섬유의 제조방법
KR20120105179A (ko) * 2011-03-15 2012-09-25 한양대학교 산학협력단 그라핀 복합 섬유 및 이의 제조 방법
KR20120107026A (ko) * 2011-03-15 2012-09-28 한양대학교 산학협력단 그라핀 섬유 및 이의 제조 방법
KR20140105442A (ko) * 2011-10-27 2014-09-01 갈모어, 인코포레이티드 복합체 그래핀 구조
JP2016531824A (ja) * 2014-04-28 2016-10-13 寧波墨西科技有限公司Ｎｉｎｇｂｏ Ｍｏｒｓｈ Ｔｅｃｈｎｏｌｏｇｙ ＣＯ．， ＬＴＤ． グラフェン複合粉体材料及びその製造方法
KR20180039329A (ko) * 2016-10-10 2018-04-18 한양대학교 산학협력단 그래핀/고분자 복합 섬유 및 이의 제조방법

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