WO2015160041A1 - 탄소나노튜브 섬유 및 그 제조방법 - Google Patents
탄소나노튜브 섬유 및 그 제조방법 Download PDFInfo
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- WO2015160041A1 WO2015160041A1 PCT/KR2014/007177 KR2014007177W WO2015160041A1 WO 2015160041 A1 WO2015160041 A1 WO 2015160041A1 KR 2014007177 W KR2014007177 W KR 2014007177W WO 2015160041 A1 WO2015160041 A1 WO 2015160041A1
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- Prior art keywords
- carbon nanotube
- strength
- fibers
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- nanotube fiber
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 268
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 247
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 247
- 239000000835 fiber Substances 0.000 title claims abstract description 179
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 54
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims description 28
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000005917 acylation reaction Methods 0.000 claims description 13
- 238000009987 spinning Methods 0.000 claims description 13
- HGEVGSTXQGZPCL-UHFFFAOYSA-N nonanedioyl dichloride Chemical compound ClC(=O)CCCCCCCC(Cl)=O HGEVGSTXQGZPCL-UHFFFAOYSA-N 0.000 claims description 9
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 8
- 125000002252 acyl group Chemical group 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000010036 direct spinning Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 150000003855 acyl compounds Chemical class 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- -1 carboxylic acid compound Chemical class 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000006199 nebulizer Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 abstract description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000005411 Van der Waals force Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 239000004971 Cross linker Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002074 nanoribbon Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
Classifications
-
- 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
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/192—Polycarboxylic acids; Anhydrides, halides or salts thereof
-
- 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
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- 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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
-
- 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
- D10B2101/00—Inorganic fibres
- D10B2101/10—Inorganic fibres based on non-oxides other than metals
- D10B2101/12—Carbon; Pitch
- D10B2101/122—Nanocarbons
Definitions
- It relates to carbon nanotube fibers and a method of manufacturing the same.
- Carbon nanotubes are nanomaterials with excellent mechanical strength, and the tensile strength of one strand is up to 150 GPa.
- carbon nanotube fibers are made up of numerous carbon nanoleubes, but they are connected between the walls and walls by van der Waals forces, weak molecular bonds.
- Physical methods include shrinking the carbon nanotube fibers by spraying a solvent on the carbon nanotube fibers or dipping the carbon nanotube fibers in a solvent. Through this, as the distance between the carbon nanotubes is narrowed to increase the van der Waals force, the strength of the carbon nanotube fibers can be increased.
- carbon nanotubes constituting the carbon nanotube fibers generally tend to have better chemical response at the ends than wall surfaces.
- the cross-link reaction reported so far is that the reaction occurs mainly at the end rather than on the carbon nanotube wall, thus remarkably improving the bonding force between the wall and the wall of the carbon nanotube.
- the tensile strength of the carbon nanotube fibers reaches only about 5 GPa in the above chemical method.
- the tensile strength is superior to> 5 GPa.
- a carbon nanotube fiber having a tensile strength exceeding 5 GPa is provided.
- the carbon nanotube fibers constitute the carbon nanotube fibers.
- Wall surfaces of the carbon nano-rubber may be cross-linked with each other.
- the crosslinked form may be a crosslinked form by acylation reaction between walls of the carbon nanotubes.
- the acylation reaction may be a single step reaction.
- the diameter of the carbon nanotube fibers may be 1 to 150, specifically 3 to 30.
- a method of preparing a carbon nanotube fiber precursor composed of carbon nanotubes is provided; Evenly dispersing a crosslinking agent in the carbon nanotube fiber precursor; And carbon nanotube fibers in which the crosslinker is evenly distributed. Heat-treating the precursor to obtain carbon nanotube fibers; wherein the obtained carbon nanotube fibers are in the form of cross-links formed between the walls of the carbon nanotubes. do.
- Preparing a carbon nanotube fiber precursor composed of carbon nanotubes may be performed by any one method of forest spinning, direct spinning, and solution spinning; , Specifically, it may be forest spinning.
- this includes preparing a substrate; On the substrate
- the substrate may include silicon.
- the carbon nanotube fiber precursor may be in the form of a carbon nanotube ribbon.
- preparing a carbon nanotube precursor consisting of carbon nanotubes may be performed in a temperature range of 600 to 1000 ° C. Specifically, it may be performed at a temperature range of 630 to 670 ° C.
- At least one selected from the group of hydrocarbons having 1 to 20 carbon atoms is selected from the group of hydrocarbons having 1 to 20 carbon atoms
- the crosslinking agent may be distributed on the surface of the carbon nanotube fiber precursor.
- the carbon nanotube fiber precursor may be soaked by immersing the tip of the carbon nanotube fiber precursor in the crosslinker in solution.
- the crosslinking agent may be one containing two or more acyl groups. Specifically, it may be one or more selected from the group containing a halogenated acyl compound and a carboxylic acid compound. More specifically, Azelaic Acid
- It may be at least one selected from the group comprising dichloride, poly acryly chloride, azelaic acid, poly acrylic acid.
- the carbon nano-leave fiber precursor is evenly distributed
- Heat treatment, 'obtaining the carbon nanotube fibers may be by a single step reaction. Specifically, it may be based on an acylation reaction.
- This may be carried out in a nitrogen or inert atmosphere.
- the heat treatment may be performed at a temperature range of 160 to 250 ° C.
- the carbon nanotube fibers obtained may have a diameter of 1 to 150.
- the tensile strength of the obtained carbon nanotube fibers may be 5 to 40 GPa, specifically 30 to 40 GPa.
- FIG. 1 is a result of Fourier transform infrared spectroscopy analysis of carbon nanotube fibers (top) and carbon nanotube fibers (bottom) prepared according to an embodiment of the present invention.
- FIG. 2 is a scanning electron micrograph of carbon nanotube fibers according to an embodiment of the present invention.
- a carbon nanotube fiber having a tensile strength exceeding 5 GPa is provided.
- the tensile strength may be greater than 100 GPa, more specifically, 20 GPa or more, and more specifically, 30 GPa or more.
- FIG. 2 is a scanning electron micrograph of carbon nanotube fibers according to an embodiment of the present invention.
- the carbon nanotube fibers constitute the carbon nanotube fibers.
- Wall surfaces of the carbon nanotubes may be cross-linked with each other.
- the crosslinking means chemically connecting each other directly or through several bonds at any position other than the terminal of the carbon chain. By forming a covalent bond stronger than van der Waals force by the crosslinking, it is possible to increase the strength of the carbon nanotube fibers.
- crosslinks formed between the walls, not the ends of the carbon nanotubes can effectively increase the shear strength between the carbon nanotubes.
- the carbon nanotube fibers can be efficiently delivered within the carbon nanotube fibers, thereby increasing the strength of the carbon nanotube fibers.
- the crosslinked form may be a crosslinked form by acylation reaction between walls of the carbon nanotubes.
- the acylated reaction reaction is a reaction reaction for substituting hydrogen contained in the organic compound with an acyl group, and a reaction reaction having better reactivity at the wall surface than the end of the carbon nanotube.
- the acylation reaction may be a single step reaction.
- crosslinking can be formed in a simple process without having to go through several steps of surface modification of carbon nanotubes.
- the carbon nanotube fiber may have a diameter of 1 to 150, specifically 3 to 30.
- Another embodiment of the present invention preparing a carbon nanotube fiber precursor consisting of carbon nanotubes; Evenly dispersing a crosslinking agent in the carbon nanotube fiber precursor; And heat treating the carbon nanotube fiber precursor in which the crosslinking agent is evenly distributed to obtain carbon nanotube fibers.
- the obtained carbon nanotube fibers are in the form of crosslinks formed between the walls of the carbon nanotubes. It provides a method for producing high strength carbon nanotube fibers.
- the carbon nanotube fiber precursor means a fiber in which the carbon nano-rubbers constituting the carbon nanotubes are aggregated in an axial direction, and specifically, all carbon nanotube ribbons, fibers, and yarns are included. It is defined as a concept.
- the carbon nanotube fiber precursor has a form in which carbon nanotubes are aligned in the axial direction, specifically, carbon nanotube ribbons in which carbon nanotubes are arranged in a film form, and carbon nanotubes in the form of fibers.
- Carbon nanotube fibers, which are aligned structures, and carbon nanotube yarns, in which carbon nanotube fibers are twisted, are defined as a concept encompassing both.
- the obtained carbon nanotube fibers is defined as carbon nanotube fibers in the form of cross-linking formed between the walls of the carbon nanotubes constituting it. That is, the carbon nanotube fiber precursor is a concept that is distinguished with respect to the formation of crosslinks between walls.
- forest spinning direct spinning
- solution spinning specifically, forest
- the forest spinning is carbon nanotubes on a substrate
- the direct spinning is a method of producing carbon nanotube fibers by synthesizing carbon nanotubes in an aerogel state, and the solution spinning is agglomeration of only carbon nanotubes from a solution in which carbon nano-leuze is dispersed. This is how you pull it out.
- the forest spinning which comprises the steps of preparing a substrate; Growing carbon nanotubes on the substrate; And extracting the carbon nanotube fiber precursor from the substrate on which the carbon nanotubes are grown.
- the substrate is a substrate having a very small surface (roughness), and may be a silicon substrate, a silicon / silicon oxide substrate. Specifically, one or more selected from the group containing alumina and iron may be deposited. see
- silicon oxide, alumina, iron may be sequentially deposited on the silicon substrate.
- the carbon nanotube fiber precursor is extracted from the substrate on which the carbon nanotubes are grown; the carbon nanotubes grown on the substrate may be stretched in one direction to be extracted in a plane form.
- the carbon nanotube fiber precursor may be in the form of a carbon nanotube ribbon.
- the carbon nanotube ribbon may be extracted in the form of a surface while pulling the end of the carbon nanotube array (array) grown perpendicular to the silicon wafer.
- carbon nanotubes can be gathered to reach bundles of tens to hundreds of nanometers of carbon nanorubbers, and these bundles can be gathered to form carbon nano-leave ribbons having very large surface areas.
- the step of preparing a carbon nano-rubber precursor consisting of carbon nanotubes may be performed in a temperature range of 600 to 1000 ° c. . If it exceeds the loocrc, the decomposition rate of acetylene gas is too fast, and the catalyst is poisoned by an excessive supply of carbon to inhibit stable carbon nanotube growth. On the other hand, if less than 600 ° C, the decomposition of the acetylene gas is not smooth, the carbon is not well supplied to the catalyst.
- the temperature range may be specifically 630 to 670 ° C.
- the step of preparing a carbon nanotube fiber precursor consisting of carbon nanotubes at least one selected from a hydrocarbon group having 1 to 20 carbon atoms may be used as a carbon source, specifically, one of acetylene, methane, ethylene It may be abnormal.
- the crosslinking agent may be distributed on the surface of the carbon nanotube fiber precursor.
- the crosslinking agent when the crosslinking agent is sprayed with an air gun on the surface of the carbon nanotube fiber precursor having a maximum surface area, the crosslinking agent may be evenly distributed between the carbon nanotube fiber precursors.
- the end of the carbon nanotube fiber precursor is immersed in the crosslinking agent in a solution state, and the crosslinking agent is
- the crosslinking agent may be one containing two or more acyl groups, specifically, may be a material containing an acyl group at both ends.
- crosslinking between the walls of the carbon nanotubes constituting the carbon nanotube fibers may be formed in a single step reaction.
- the crosslinking agent may be one or more selected from the group containing a halogenated acyl compound and a carboxylic acid compound as a highly reactive material.
- the azelaic acid dichloride is in a liquid state at room temperature.
- both ends contain a functional group, a single step
- Crosslinks can be formed.
- a compound having a carboxylic acid or a COC1 functional group on both sides regardless of the number of carbons, selected from the group containing azelaic acid dichloride, poly acryly chloride, azelaic acid, polyacrylic acid There may be more than one.
- the carbon nanotube fiber precursor is evenly distributed
- Heat-treating to obtain carbon nanotube fibers is by a single step reaction Can be. Specifically, it may be based on an acylation reaction. Detailed description of the crosslinking and acylation reaction is as described above.
- the heat treatment may be performed at a temperature range of 160 to 250 ° C. If the cross-linking agent exceeds 250 ° C., the cross-linking agent is decomposed and crosslinking hardly occurs. If the cross-linking agent is less than 160 ° C., the energy is not sufficiently separated to cause a reaction.
- the diameter of the carbon nano-leave fibers obtained may be 1 to 150, specifically 3 to 30.
- the tensile strength of the obtained carbon nanotube fibers may be 5 to 40 GPa. Specifically, it may be 20 to 40 GPa, and more specifically 30 to 40 GPa.
- preferred examples and comparative examples of the present invention are described. However, the following examples are only preferred examples of the present invention and the present invention is not limited to the following examples.
- Forest spinning was used to form carbon nano ribbon ribbons on the substrate.
- silicon As the substrate, silicon (Siltron Inc. Korea, ⁇ 100> direction, thickness: 660-690 ⁇ ) on which 300 nm of silicon oxide (Si0 2 ) was deposited was used, and on the substrate, aluminum oxide ( 10 nm of A1 2 0 3 ) was deposited on the e-beam
- Iron (Fe) was deposited by l nm deposition.
- the substrate was placed in the center of a tubular furnace (Lindberg Blue M, HTF55322, tube diameter 4 cm, length 70 cm), and then argon (Ar) was flowed at 500 sccm to raise the temperature. After reaching the reaction temperature of 670 ° C., 286 sccm of argon, 96 sccm of hydrogen, and 19 sccm of acetylene were flowed for 3 minutes to synthesize a carbon nanotube array. Subsequently, the hydrogen and acetylene supply was stopped, and the mixture was cooled to room temperature in an argon atmosphere, and then the substrate on which the carbon nanotube array was synthesized was removed from the tube. Then, the carbon nanotube ribbons having a maximum surface area were obtained by stretching the end portions of the carbon nano-leave array in one direction while pulling them in one direction. b) crosslinker injection
- azelaic acid dichloride in a liquid state was sprayed onto the surface of the prepared carbon nanotube ribbon by using an air gun (BLUE BIRD).
- the azelaic acid dichloride is in a liquid state at room temperature
- the surface area is maximized by spraying it
- Carbon nanotubes could be evenly distributed between the carbon nanotubes in the ribbon. c) acylation reaction
- the carbon nano-leave ribbon with evenly distributed azelaic acid dichloride was placed in a furnace (Lindberg Blue M, HTF55322, tube diameter 4 cm, length 70 cm) and heated at 16 C C in an argon atmosphere.
- azelaic acid dichloride since the azelaic acid dichloride was very reactive, it could react with the aromatic ring of the carbon nanotube wall to cause acylation reaction.
- the azelaic acid dichloride also contains functional groups at both ends. Therefore, crosslinking could be formed in a single step.
- One of the carbon nanotube fibers having a length of 100 mm prepared in the above example was fixed, and the other was attached to the motor. At this time, the bottom and the angle of the fiber was fixed to 10 to 15 degrees.
- Carbon nanotube fibers ' were prepared.
- the carbon nanotube fiber according to the comparative example does not have a specific functional group peak, and after the carbon nanotube fiber according to the embodiment, it can be seen that a peak due to an acyl functional group appears.
- FIG. 2 is a scanning electron micrograph of a carbon nanotube fiber according to the embodiment.
- the carbon nanotube fibers are carbon nanotube bundles.
- Figure 4 is a measurement result of the tensile strength for the carbon nanotube fibers according to the comparative example.
- the tensile strength of the carbon nanotube fibers according to the comparative example is 0.4 GPa.
- the tensile strength of the carbon nanotube fibers according to the embodiment is confirmed to be up to 36 GPa.
- the carbon nanotube fiber according to the embodiment of the present invention is conventional It can be seen that the carbon nanotube fibers are very high strength. This is because the cross-linking between the wall surfaces of the carbon nanotubes constituting the carbon nanotube fibers is formed by the acylation reaction, so that the shear strength between the carbon nanotubes can be increased.
- the present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Inorganic Fibers (AREA)
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Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016563031A JP6368797B2 (ja) | 2014-04-17 | 2014-08-04 | 炭素ナノチューブ繊維およびその製造方法 |
CN201480077980.3A CN106232879B (zh) | 2014-04-17 | 2014-08-04 | 碳纳米管纤维及其制造方法 |
US15/304,192 US20170044689A1 (en) | 2014-04-17 | 2014-08-04 | Carbon nanotube fiber and method for producing the same |
AU2014391194A AU2014391194B2 (en) | 2014-04-17 | 2014-08-04 | Carbon nanotube fiber and manufacturing method thereof |
EP14889594.9A EP3133190A4 (en) | 2014-04-17 | 2014-08-04 | Carbon nanotube fiber and manufacturing method thereof |
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JP (1) | JP6368797B2 (ko) |
KR (1) | KR101615338B1 (ko) |
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JP2019532193A (ja) * | 2017-02-03 | 2019-11-07 | エルジー・ケム・リミテッド | カーボンナノチューブ繊維の製造方法及びこれにより製造されたカーボンナノチューブ繊維 |
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KR102002909B1 (ko) * | 2015-12-16 | 2019-07-26 | 주식회사 엘지화학 | 인장 강도와 내열성이 향상된 카본 나노튜브 섬유 및 이의 제조 방법 |
KR102069411B1 (ko) * | 2016-10-31 | 2020-01-22 | 주식회사 엘지화학 | 인장강도가 향상된 카본나노튜브 섬유 및 이의 제조방법 |
KR102098989B1 (ko) | 2017-01-04 | 2020-04-08 | 주식회사 엘지화학 | 탄소나노튜브 섬유 집합체 강도 조절 방법 |
KR102113382B1 (ko) * | 2017-07-28 | 2020-05-20 | 주식회사 엘지화학 | 강도가 향상된 탄소 나노튜브 섬유 집합체의 제조 방법 |
KR101900331B1 (ko) | 2017-07-28 | 2018-09-20 | 주식회사 화인지오텍 | 다겹 보온커튼 및 그 제조방법 |
CN109455694B (zh) * | 2018-12-10 | 2020-11-03 | 深圳烯湾科技有限公司 | 改性碳纳米管阵列、碳纳米管纤维及其制备方法和应用 |
CN114644337B (zh) * | 2022-03-11 | 2023-06-02 | 电子科技大学 | 一种等离子体诱导高效催化碳纳米管阵列的方法 |
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- 2014-08-04 EP EP14889594.9A patent/EP3133190A4/en active Pending
- 2014-08-04 CN CN201480077980.3A patent/CN106232879B/zh active Active
- 2014-08-04 US US15/304,192 patent/US20170044689A1/en not_active Abandoned
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Also Published As
Publication number | Publication date |
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JP2017514030A (ja) | 2017-06-01 |
CN106232879B (zh) | 2021-07-16 |
JP6368797B2 (ja) | 2018-08-01 |
KR101615338B1 (ko) | 2016-04-25 |
KR20150120250A (ko) | 2015-10-27 |
US20170044689A1 (en) | 2017-02-16 |
AU2014391194A1 (en) | 2016-11-17 |
EP3133190A1 (en) | 2017-02-22 |
EP3133190A4 (en) | 2017-12-06 |
AU2014391194B2 (en) | 2018-12-20 |
CN106232879A (zh) | 2016-12-14 |
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