KR20220134922A - A Manufacturing method of carbon fibers from lyocell fiber - Google Patents
A Manufacturing method of carbon fibers from lyocell fiber Download PDFInfo
- Publication number
- KR20220134922A KR20220134922A KR1020210040200A KR20210040200A KR20220134922A KR 20220134922 A KR20220134922 A KR 20220134922A KR 1020210040200 A KR1020210040200 A KR 1020210040200A KR 20210040200 A KR20210040200 A KR 20210040200A KR 20220134922 A KR20220134922 A KR 20220134922A
- Authority
- KR
- South Korea
- Prior art keywords
- lyocell
- fiber
- carbon fiber
- manufacturing
- fabric
- Prior art date
Links
- 229920000433 Lyocell Polymers 0.000 title claims abstract description 78
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 59
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 23
- 238000003763 carbonization Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 230000005855 radiation Effects 0.000 claims abstract description 15
- 238000010000 carbonizing Methods 0.000 claims abstract description 8
- 239000004744 fabric Substances 0.000 claims description 21
- 239000000835 fiber Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 16
- 229920000578 graft copolymer Polymers 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 229920002678 cellulose Polymers 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229920000297 Rayon Polymers 0.000 claims description 4
- 239000002964 rayon Substances 0.000 claims description 4
- 238000010894 electron beam technology Methods 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 238000010884 ion-beam technique Methods 0.000 claims description 2
- -1 polyethylimine Chemical compound 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- 229920003043 Cellulose fiber Polymers 0.000 claims 1
- 229920001661 Chitosan Polymers 0.000 claims 1
- 229920000742 Cotton Polymers 0.000 claims 1
- 230000001678 irradiating effect Effects 0.000 claims 1
- 230000006641 stabilisation Effects 0.000 abstract description 9
- 238000011105 stabilization Methods 0.000 abstract description 9
- 239000003431 cross linking reagent Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 6
- 229920002239 polyacrylonitrile Polymers 0.000 description 6
- 238000002411 thermogravimetry Methods 0.000 description 6
- 239000002243 precursor Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- IVNPXOUPZCTJAK-UHFFFAOYSA-N 4-methylmorpholin-4-ium;hydroxide Chemical compound O.CN1CCOCC1 IVNPXOUPZCTJAK-UHFFFAOYSA-N 0.000 description 1
- 229920000875 Dissolving pulp Polymers 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000021962 pH elevation Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Images
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
- D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
-
- 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
- D06M10/001—Treatment with visible light, infrared or ultraviolet, X-rays
-
- 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
- D06M10/008—Treatment with radioactive elements or with neutrons, alpha, beta or gamma rays
-
- 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
- D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
-
- 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
- D10B2401/063—Load-responsive characteristics high strength
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Fibers (AREA)
Abstract
Description
본 발명은 라이오셀 섬유를 탄화함으로써, 탄소섬유를 얻는 제조방법에 관한 것으로서, 원사인 라이오셀 섬유를 폴리아크릴아마이드(polyacrylamide, PAM)용액에 침지한 후 방사선, 가열, 가교제를 통해서 라이오셀 섬유에 그라프트화하고, 일정한 온도 범위에서 열안정화를 거쳐 난염화한 후, 고온 탄화처리를 통하여 탄소섬유를 얻는 제조 방법에 관한 것이다. The present invention relates to a manufacturing method for obtaining carbon fibers by carbonizing lyocell fibers. After immersing lyocell fibers, which are yarns, in a polyacrylamide (PAM) solution, radiation, heating, and a crosslinking agent to the lyocell fibers. It relates to a manufacturing method of obtaining carbon fibers through grafting, heat stabilization in a certain temperature range, and flame retardancy, and then high-temperature carbonization treatment.
탄소 섬유는 자동차, 항공 분야나, 양질의 스포츠 용품, 풍력터빈 블레이드 등 첨단 복합재료의 보강재로 널리 사용되고 있다. 탄소 섬유의 전구체로는 폴리아크릴로니트릴 (polyacrylonitrile, PAN), 피치, 셀룰로오스로 분류되는데, 그 중, PAN 섬유는 고성능 탄소섬유의 전구체로 98% 이상을 차지한다. 그러나, PAN 섬유는 화석연료로부터 얻어지기 때문에 탄화하는 동안 다량의 유독 가스 발생 및 사용 후 폐기 처리에 대한 큰 단점을 가지고 있다. 게다가, PAN 섬유는 가격이 비싸고 국제유가 변동에 따라 다양하게 변할 수 있다. 따라서, 친환경적이면서 값이 저렴한 전구체에 대한 연구가 필요하다. Carbon fiber is widely used as a reinforcement for high-tech composite materials such as automobiles, aviation, high-quality sporting goods, and wind turbine blades. As a precursor of carbon fiber, polyacrylonitrile (PAN), pitch, and cellulose are classified, among which, PAN fiber is a precursor of high-performance carbon fiber and accounts for more than 98%. However, since PAN fibers are obtained from fossil fuels, they have major disadvantages in terms of generation of a large amount of toxic gas during carbonization and disposal after use. In addition, PAN fibers are expensive and can vary widely according to fluctuations in international oil prices. Therefore, there is a need for research on environmentally friendly and inexpensive precursors.
셀룰로오스는 목재나 비목재로부터 얻어지는 지구상에서 가장 풍부한 유기 물질이면서, 가장 오래된 탄소섬유의 전구체이지만, 수율 및 기계적 강도가 낮은 단점이 있다. 그럼에도 불구하고, 셀룰로오스계 탄소 섬유는 원료의 안정한 공급, 경제성 및 친환경성으로 인해 PAN계 탄소섬유 대신할 수 있도록 수율과 기계적 강도를 향상시키기 위한 연구가 계속되고 있다. Cellulose is the most abundant organic material on earth obtained from wood or non-wood, and is the oldest precursor of carbon fiber, but has the disadvantage of low yield and low mechanical strength. Nevertheless, research to improve the yield and mechanical strength of the cellulosic carbon fiber to replace the PAN-based carbon fiber due to the stable supply of raw materials, economy and eco-friendliness is continuing.
탄소섬유의 전구체로 사용되는 셀룰로오스는 레이온 섬유와 라이오셀 섬유가 대표적이다. 레이온 섬유는 목재펄프의 섬유소를 재생하여 만든 재생섬유로서 알칼리화, 크산토겐산염화와 같은 복잡한 전처리공정이 동반되고 다양한 부산물이 발생된다. 한편, 라이오셀 섬유는 용제인 N-methylmorpholine-N-oxide(NMMO) 단독 또는 NMMO와 물을 혼합한 용액에 셀룰로오스를 직접 용해하여 얻어진 섬유로서, 단면이 동그랗고, 가늘고 긴 모양을 가진 섬유이다. 비교적 간단한 유기 용매 방사를 사용하므로 간단하고, 친환경적으로 제조가 가능하다. Cellulose used as a precursor of carbon fiber is representative of rayon fiber and lyocell fiber. Rayon fiber is a regenerated fiber made by regenerating fiber from wood pulp, and it is accompanied by complex pretreatment processes such as alkalinization and xanthogenation, and various by-products are generated. On the other hand, lyocell fiber is a fiber obtained by directly dissolving cellulose in a solvent, N -methylmorpholine- N -oxide (NMMO) alone or in a solution of NMMO and water, and has a round cross-section and a long, thin fiber. Since a relatively simple organic solvent spinning is used, it is simple and environmentally friendly to manufacture.
다만, 라이오셀 섬유와 레이온 섬유와 같은 셀룰로오스는 탄소 수율과 강도가 매우 낮기 때문에, 탄소 섬유로 전환하기 전에 난연제 처리와 같은 전처리를 수행하여 왔다. However, since cellulose such as lyocell fiber and rayon fiber has very low carbon yield and strength, pretreatment such as flame retardant treatment has been performed before conversion to carbon fiber.
이에, 본 발명은 라이오셀계 섬유를 이용한 탄소섬유를 얻되, 탄소수율과 강도를 개선하기 위한 새로운 제조방법을 착안하게 되었다. Accordingly, the present invention was conceived of a new manufacturing method for obtaining carbon fibers using lyocell-based fibers, and improving carbon yield and strength.
본 발명은 셀룰로오스를 이용한 라이오셀계 섬유로부터 탄소섬유를 제조함에 있어서 탄소섬유의 물리적 강도와 탄화 수율을 높일 수 있는 라이오셀 섬유를 이용한 탄소섬유 제조방법을 제공하는 것을 목적으로 한다. An object of the present invention is to provide a carbon fiber manufacturing method using lyocell fibers capable of increasing the physical strength and carbonization yield of carbon fibers in manufacturing carbon fibers from lyocell-based fibers using cellulose.
본 발명은 라이오셀을 이용하여 탄소섬유를 얻기 위해 난연제 처리를 대신할 수 있는 새로운 처리방법을 포함하는 탄소섬유 제조방법을 제공하는 것을 목적으로 한다. An object of the present invention is to provide a carbon fiber manufacturing method including a new treatment method that can replace the flame retardant treatment to obtain carbon fibers using lyocell.
상기 목적을 달성하기 위하여, 본 발명은 In order to achieve the above object, the present invention
- 라이오셀 섬유에 그라프트 고분자 용액을 침지하는 단계(S1);- Immersion of the graft polymer solution in the lyocell fiber (S1);
- 그라프트 고분자용액이 침지된 라이오셀 섬유에 방사선, 또는 가열을 통해서 그라프트화 하는 단계(S2);- Grafting the lyocell fiber immersed in the graft polymer solution through radiation or heating (S2);
- 그라프트화된 라이오셀 섬유를 건조하는 단계(S3);- drying the grafted lyocell fibers (S3);
- 상기 건조된 라이오셀 섬유를 일정한 온도 구간에서 열안정화하여 난염화하는 단계(S4); 및- Heat-stabilizing the dried lyocell fiber in a constant temperature section to make it flame retardant (S4); and
- 상기 열안정화된 라이오셀 섬유를 고온에서 탄화하는 단계(S5)를 포함하는 라이오셀 섬유를 이용한 탄소섬유 제조방법이다. - It is a carbon fiber manufacturing method using the lyocell fiber comprising the step (S5) of carbonizing the thermally stabilized lyocell fiber at a high temperature.
본 발명은 라이오셀 섬유나 직물을 이용하여 탄소 섬유 또는 직물로 제조하기 위하여 방사선 또는 가열을 이용하여 라이오셀 섬유에 폴리아크릴아마이드를 그라프팅하고, 이후 열안정화 공정을 통해 간소화하고 빠른 시간 내에 섬유를 안정화시킴으로써, 탄소섬유의 물리적 강도와 탄화 수율이 현저하게 개선되었다. The present invention grafts polyacrylamide to lyocell fibers by using radiation or heating to produce carbon fibers or fabrics using lyocell fibers or fabrics, and then simplifies through a thermal stabilization process and produces fibers within a short time. By stabilizing, the physical strength and carbonization yield of carbon fibers were remarkably improved.
도 1은 본 발명의 일실시예에 따른 라이오셀계 탄소섬유 제조방법에 대한 간략도이다.
도 2는 본 발명의 일실시예에 따라 제조된 라이오셀계 탄소직물 사진이다.
도 3은 본 발명의 일실시예에 따라 제조된 라이오셀 탄소섬유의 열중량 분석 (TGA) 그래프이다.
도 4는 본 발명의 일실시예에 따라 제조된 라이오셀 탄소섬유의 주사 전자현미경 (SEM) 사진이다.
도 5는 본 발명의 일실시예에 따라 제조된 라이오셀 탄소섬유의 인장강도 측정값 그래프이다. 1 is a simplified diagram of a lyocell-based carbon fiber manufacturing method according to an embodiment of the present invention.
2 is a photograph of a lyocell-based carbon fabric prepared according to an embodiment of the present invention.
3 is a thermogravimetric analysis (TGA) graph of the lyocell carbon fiber prepared according to an embodiment of the present invention.
4 is a scanning electron microscope (SEM) photograph of a lyocell carbon fiber prepared according to an embodiment of the present invention.
5 is a graph of the tensile strength measurement value of the lyocell carbon fiber prepared according to an embodiment of the present invention.
본 발명의 라이오셀 섬유를 이용한 탄소섬유 제조방법의 바람직한 실시예는 기본적으로 다음과 같은 공정을 의한다. 여기서 라이오셀 섬유라 함은 라이오셀계 섬유 뿐만 아니라, 직물을 포함하는 것을 의미하고 탄화에 의해서 생성된 탄소섬유라 함은 탄소직물을 포함하는 것을 의미한다. 본 발명에 따른 라이오셀 섬유를 이용한 탄소섬유의 제조방법은 각 단계별 순서를 도 1에 도시하였고 이를 참조하여 설명한다.A preferred embodiment of the carbon fiber manufacturing method using the lyocell fiber of the present invention is basically by the following process. Here, the lyocell fiber means including not only the lyocell-based fiber but also the fabric, and the carbon fiber produced by carbonization means including the carbon fabric. The manufacturing method of carbon fiber using lyocell fiber according to the present invention is illustrated in FIG. 1 for each step sequence and will be described with reference to this.
- 라이오셀 섬유에 그라프트 고분자 용액을 침지하는 단계(S1);- Immersion of the graft polymer solution in the lyocell fiber (S1);
- 그라프트 고분자용액이 침지된 라이오셀 섬유에 방사선 또는 가열을 통해서 그라프트화 하는 단계(S2);- Grafting the lyocell fiber immersed in the graft polymer solution through radiation or heating (S2);
- 그라프트화된 라이오셀 섬유를 건조하는 단계(S3);- drying the grafted lyocell fibers (S3);
- 상기 건조된 라이오셀 섬유를 일정한 온도 구간에서 열안정화하여 난염화하는 단계(S4); 및- Heat-stabilizing the dried lyocell fiber in a constant temperature section to make it flame retardant (S4); and
- 상기 열안정화된 라이오셀 섬유를 고온에서 탄화하는 단계(S5)를 포함하는 것을 특징으로 하는 라이오셀 섬유를 이용한 탄소섬유 제조방법이다. - Carbon fiber manufacturing method using lyocell fiber, characterized in that it comprises the step (S5) of carbonizing the heat-stabilized lyocell fiber at a high temperature.
상기 탄소섬유 제조방법에 대해서 아래에서 구체적으로 설명한다. The carbon fiber manufacturing method will be described in detail below.
- 1 단계(S1)는 라이오셀 섬유(또는 직물)를 가교제인 그라프트 고분자 용액에 침지하는 단계로서, 침지한 상태 그대로를 이용할 수 있으며 또는 롤러(roller) 등을 이용하여 라이오셀 섬유 또는 직물로부터 그라프트 고분자 용액을 적당량 제거한 상태를 이용할 수 있다. - Step 1 (S1) is a step of immersing the lyocell fiber (or fabric) in the graft polymer solution, which is a crosslinking agent. A state in which an appropriate amount of the graft polymer solution has been removed may be used.
상기 그라프트 고분자 용액은 폴리아크릴아마이드, 아크릴산계 유도체, 메타크릴로니트릴, 메타크릴산글리시딜, 구연산. 에피클로히드린, 폴리에틸이민, 글루타알데하이드를 포함하는 군으로부터 1종 이상 선택될 수 있으나, 바람직하게는 폴리아크릴아마이드 용액을 사용하며 본원 발명의 실시예로서 사용하였다. 폴리아크릴아마이드 용액은 0.005 중량%~ 4 중량% 일 수 있으나, 0.05 중량%~ 0.5 중량%인 것이 바람직하다. 0.05중량% 이하이면 그 효과를 나타내기 어렵고, 0.5중량% 이상이면, 점도가 증가하여 탄소섬유가 서로 엉겨붙게 되어 섬유의 분리가 곤란하게 된다. The graft polymer solution is polyacrylamide, an acrylic acid derivative, methacrylonitrile, glycidyl methacrylate, citric acid. At least one may be selected from the group comprising epichlorohydrin, polyethylimine, and glutaraldehyde, but preferably, a polyacrylamide solution is used and used as an example of the present invention. The polyacrylamide solution may be 0.005 wt% to 4 wt%, but preferably 0.05 wt% to 0.5 wt%. If it is less than 0.05% by weight, it is difficult to exhibit the effect, and if it is more than 0.5% by weight, the viscosity increases and the carbon fibers become agglomerated with each other, making it difficult to separate the fibers.
- 2단계는 상기와 같이 그라프트 고분자 용액이 침지된 라이오셀 섬유를 방사선 또는 가열을 통해서 그라프트화하는 단계이다. - Step 2 is a step of grafting the lyocell fiber immersed in the graft polymer solution through radiation or heating as described above.
상기 라이오셀에 고분자를 그라프트화하는 방사선으로는 감마선, 전자선, 이온빔, 중성자빔, 자외선 및 X선 등을 사용할 수 있으며, 방사선 조사선량은 50 kGy ~ 500 kGy 일 수 있으나, 바람직하게는 100 kGy~300 kGy인 것이 적당하다. 한편 열에 의해서 그라프트화 하는 것은 80 ℃이상에서 가열하는 것이 바람직하다. As radiation for grafting the polymer to the lyocell, gamma rays, electron beams, ion beams, neutron beams, ultraviolet rays and X-rays may be used, and the radiation dose may be 50 kGy to 500 kGy, but preferably 100 kGy to 300 kGy is suitable. On the other hand, for grafting by heat, it is preferable to heat it at 80°C or higher.
- 방사선 조사 또는 가열에 의해서 그라프트화된 라이오셀 섬유를 건조하는 단계 (S3);- Drying the grafted lyocell fibers by irradiation or heating (S3);
폴리아크릴아마이드가 그라프트화된 라이오셀 섬유를 건조하는 단계로서, 그라프트화된 라이오셀 섬유는 초저온 냉동고에서 냉동 동결 건조를 하거나 자연, 실온, 가열 건조하는 것 중 어느 하나 선택하여 건조할 수 있으나, 바람직하게는 동결 건조하는 것이다.As a step of drying the lyocell fiber grafted with polyacrylamide, the grafted lyocell fiber may be freeze-dried in a cryogenic freezer or dried by selecting any one of natural, room temperature, and heat-drying, but preferably The preferred method is freeze-drying.
- 상기 건조된 라이오셀 섬유를 일정한 온도 구간에서 열안정화하는 단계 (S4); - Thermal stabilization of the dried lyocell fiber in a constant temperature section (S4);
상기에서 건조된 라이오셀 섬유를 일정한 온도 구간에서 열안정화를 위한 열처리단계로서, 상기 열처리단계는 분당 1~10 ℃로 하여 200~300 ℃에서 30분에서 3시간 동안 수행할 수 있다. 상기 단계들을 통하여 라이오셀은 탄화공정을 수행하는데 적합한 분자구조를 갖추게 된다. As a heat treatment step for thermal stabilization of the dried lyocell fiber in a constant temperature section, the heat treatment step may be performed at 200 to 300 ° C. for 30 minutes to 3 hours at 1 to 10 ° C. per minute. Through the above steps, the lyocell has a molecular structure suitable for carrying out the carbonization process.
- 상기 열안정화된 라이오셀 섬유를 고온에서 탄화하는 단계 (S5)를 포함한다.- Carbonizing the thermally stabilized lyocell fiber at a high temperature (S5).
상기 탄화단계는 불활성 분위기 가운데서 라이오셀 섬유 또는 직물을 탄화시키는 단계로서, 상기 탄화공정은 500~2500 ℃의 온도로 가열하여 진행되며, 승온속도는 분당 1~10℃로 하여 진행되되 1400 ℃이상 온도까지 승온하는 것이 바람직하다. 가급적 승온속도를 느리게 하는 것이 바람직하지만 승온속도가 너무 느리면 에너지 소비가 증가되는 문제가 있다. The carbonization step is a step of carbonizing lyocell fibers or fabrics in an inert atmosphere, and the carbonization process is performed by heating to a temperature of 500 to 2500 ℃, and the temperature increase rate is 1 to 10 ℃ per minute. It is preferable to raise the temperature to It is preferable to slow the temperature increase rate as much as possible, but if the temperature increase rate is too slow, there is a problem in that energy consumption is increased.
상기 단계들의 제조공정 중에서 그라프트화 농도, 방사선 조사량, 그리고 열안정화 온도 및 시간에 따라 라이오셀계 탄소섬유의 강도와 탄화수율이 결정된다. In the manufacturing process of the above steps, the strength and carbonization yield of the lyocell-based carbon fiber are determined according to the grafting concentration, the radiation dose, and the thermal stabilization temperature and time.
이하, 본 발명의 실시예를 통해 더욱 상세히 설명한다. 단 하기 실시예는 본발명을 예시하는 것일 뿐, 본 발명의 내용이 하기 실시 예에 한정되는 것은 아니다.Hereinafter, it will be described in more detail through examples of the present invention. However, the following examples are only illustrative of the present invention, and the content of the present invention is not limited to the following examples.
<탄소섬유 비교 실시예><Comparative Example of Carbon Fiber>
- 폴리아크릴아마이드 용액을 0.05, 0.1, 0.5, 1, 2, 그리고 4 중량% 농도로 준비하고 라이오셀 직물을 침지한 후 모두 동일하게 100kGy의 전자선량으로 조사하여 5가지의 샘플을 준비하였다. 본 비교 실시예에서는 용이한 탄소섬유의 제조를 위하여 라이오셀 직물을 사용하였다. - Polyacrylamide solutions were prepared at concentrations of 0.05, 0.1, 0.5, 1, 2, and 4% by weight, and after immersing the Lyocell fabric, all of them were irradiated with an electron dose of 100 kGy in the same manner to prepare 5 samples. In this comparative example, a lyocell fabric was used for easy production of carbon fibers.
- 전자선이 조사됨으로써 폴리아크릴아마이드가 그라프트화된 라이오셀 직물을 초저온 냉동고에서 얼린 후 동결 건조하였다.- The lyocell fabric grafted with polyacrylamide by irradiation with electron beams was frozen in a cryogenic freezer and then freeze-dried.
- 선택적으로 상기 건조된 샘플들은 분당 10℃로 승온한 후, 250 ℃에서 1시간 열안정화 하였다. - Optionally, the dried samples were heated to 10 °C per minute and then thermally stabilized at 250 °C for 1 hour.
- 열적 안정화단계를 거치지 않은 샘플들과 열적으로 안정화처리된 샘플들을 비교하기 위해서 각각에 대해서 질소분위기하에서 탄화하였다. 바람직하게는 분당 10 ℃의 승온속도로 1400 ℃까지 승온시키는 것이 강도를 크게 하는데 도움이 되지만, 위 실험에서는 1000 ℃까지 승온시킨 후 탄화하여 탄소직물을 제조하였다. - In order to compare samples not subjected to thermal stabilization and samples subjected to thermal stabilization, each was carbonized under nitrogen atmosphere. Preferably, raising the temperature to 1400 °C at a heating rate of 10 °C per minute helps to increase the strength, but in the above experiment, the carbon fabric was prepared by carbonization after raising the temperature to 1000 °C.
- 그리고 이와 같은 공정에 의해서 제조된 각각의 라이오셀계 탄소직물에 대해서 비교실험하였다. - And comparative experiments were conducted for each lyocell-based carbon fabric manufactured by the same process.
<탄소섬유 비교실험><Carbon Fiber Comparative Experiment>
TGA 분석TGA analysis
방사선을 경유하여 폴리아크릴아마이드가 그라프트화되고, 열안정화된 직물의 탄화율을 알아보기 위하여 TGA 분석을 실시하였다. TGA analysis was performed to determine the carbonization rate of the polyacrylamide grafted and heat-stabilized fabrics via radiation.
도 3의 TGA분석 그래프에서 보이는 바와 같이, 그라프트화가 없는 기본 라이오셀 직물을 탄화하는 경우, 300 ℃에서 격하게 중량감소를 보이다가 600 ℃에서 완전한 중량 감소가 발생함을 알 수 있으며, 이는 탄화에 의해서 탄소섬유를 생성할 수 없음을 말한다. As shown in the TGA analysis graph of FIG. 3, when carbonizing the basic lyocell fabric without grafting, it can be seen that the weight loss is sharply reduced at 300 ° C. It means that carbon fiber cannot be produced by
반면, 폴리아크릴아마이드가 그라프화된 라이오셀 직물은 방사선 조사를 통해서 1000 ℃에서 탄화수율이 10%에서 20%까지 증가함을 보여주었다(도 3b 참조). On the other hand, the lyocell fabric grafted with polyacrylamide showed an increase in carbonization yield from 10% to 20% at 1000 °C through irradiation (see Fig. 3b).
한편, 도 3c에서 보여주듯이 열처리에 의한 열안정화처리에 의해서 탄화수율이 증대됨과 함께 중량감소를 현저하게 완화할 수 있음을 알 수 있다. 예로 250℃에서 1시간동안 열처리한 후 TGA를 분석한 결과 탄화수율이 증가하고 중량감소가 완화되었는데, 특히 폴리아크릴아마이드가 증가할수록 40%에서 55%까지의 탄화수율이 증가하였고 중량감소도 350℃~ 650℃사이에서 서서히 나타났다. On the other hand, as shown in Fig. 3c, it can be seen that the carbonization yield is increased and the weight reduction can be significantly alleviated by the thermal stabilization treatment by heat treatment. For example, after heat treatment at 250°C for 1 hour, TGA analysis showed that the carbonization yield increased and the weight loss was alleviated. It appeared slowly between ~650 °C.
2. SEM 이미지2. SEM image
도 4는 방사선을 경유하여 폴리아크릴아마이드가 그라프화 된 라이오셀 직물로부터 얻은 탄소 섬유의 단면과 표면의 사진이다. Figure 4 is a photograph of the cross-section and surface of the carbon fiber obtained from the polyacrylamide grafted lyocell fabric via radiation.
이를 통해서, 0.5 중량% 이하의 폴리아크릴아마이드가 그라프화 된 라이오셀 직물로 얻은 탄소섬유들은 둥글고 단단한 단면과 매끈한 표면을 가지면서 섬유끼리 분리가 될 수 있음을 볼 수 있었으나, 1.0 중량 % 이상의 방사선을 경유하여 폴리아크릴아마이드가 그라프화된 라이오셀 직물의 단면은 대체로 둥글지만 표면은 폴리아크릴아마이드가 껍질이 벗겨지는 것처럼 보이거나 2 중량%나 4 중량% 경우 섬유끼리 붙어있음을 볼 수 있었다. 이는 섬유의 기계적 강도 값에 영향을 줄 것이라 예측이 되는 부분이다.Through this, it could be seen that the carbon fibers obtained from the Lyocell fabric in which 0.5 wt% or less of polyacrylamide was grafted could be separated from each other while having a round, hard cross-section and smooth surface. Although the cross-section of the lyocell fabric grafted with polyacrylamide via the passageway is generally round, the surface of the polyacrylamide appears to be peeled off, or in the case of 2 wt% or 4 wt%, it can be seen that the fibers are attached to each other. This is the part that is expected to affect the mechanical strength value of the fiber.
3. 기계적 강도3. Mechanical strength
도 5는 방사선을 경유하여 폴리아크릴아마이드가 그라프트화된 라이오셀 직물로 얻은 탄소 섬유의 기계적 강도를 나타내었다. Figure 5 shows the mechanical strength of the carbon fiber obtained from the polyacrylamide grafted lyocell fabric via radiation.
폴리아크릴아마이드 0.5중량% 이하까지 그라프트화된 라이오셀의 탄소섬유는 농도가 증가할수록 강도값이 증가하여 0.5중량%의 폴리아크릴아마이드로 그라프트화된 라이오셀 탄소섬유의 강도 값은 1.39 GPa까지 나타내었다. The strength value of the lyocell carbon fiber grafted to 0.5 wt% of polyacrylamide or less increased as the concentration increased, and the strength value of the lyocell carbon fiber grafted with 0.5 wt% of polyacrylamide was up to 1.39 GPa. .
1.0중량% 폴리아크릴아마이드로 그라프트화된 라이오셀의 탄소섬유는 SEM이미지에서 보는 바와 같이 약간 높은 점도로 인하여 섬유를 분리하는 작업에서 손상을 받아 강도값이 감소하였다. As shown in the SEM image, the carbon fiber of the lyocell grafted with 1.0 wt% polyacrylamide was damaged in the operation of separating the fiber due to a slightly high viscosity, and the strength value decreased.
한편 2중량%와 4중량% 폴리아크릴아마이드로 그라프트화된 라이오셀의 탄소섬유는 높은 점도로 인해 섬유의 붙음 현상이 발생하게 되고 한가닥 섬유를 추출할 수 없어서 강도 측정이 불가하였다. On the other hand, the carbon fibers of the lyocell grafted with 2% by weight and 4% by weight of polyacrylamide had a high viscosity, which caused the fibers to stick, and it was impossible to measure the strength because the single fibers could not be extracted.
Claims (10)
- 그라프트 고분자용액이 침지된 라이오셀 섬유 또는 직물에 방사선을 조사하거나 열을 가해 그라프트화하는 단계(S2);
- 상기 그라프트화된 라이오셀 섬유 또는 직물을 건조하는 단계 (S3);
- 상기 건조된 라이오셀 섬유 또는 직물을 일정한 온도 구간에서 열안정화하는 단계 (S4); 및
- 상기 열안정화된 라이오셀 섬유 또는 직물을 고온에서 탄화하는 단계 (S5)를 포함하는 것을 특징으로 하는 라이오셀 섬유를 이용한 탄소섬유 제조방법.
- Immersion of the graft polymer solution in the lyocell fiber or fabric (S1);
- Grafting by irradiating radiation or heat to the lyocell fiber or fabric immersed in the graft polymer solution (S2);
- drying the grafted lyocell fiber or fabric (S3);
- Heat stabilizing the dried lyocell fiber or fabric in a constant temperature section (S4); and
- Carbon fiber manufacturing method using lyocell fiber, characterized in that it comprises the step (S5) of carbonizing the heat-stabilized lyocell fiber or fabric at a high temperature.
상기 그라프트 고분자는 폴리아크릴아마이드, 아크릴산계 유도체, 메타크릴로니트릴, 메타크릴산글리시딜, 구연산. 에피클로히드린, 폴리에틸이민, 글루타알데하이드를 포함하는 군으로부터 선택되는 1종 이상인 것을 특징으로 하는 라이오셀 섬유를 이용한 탄소섬유 제조방법.
The method of claim 1,
The graft polymer is polyacrylamide, an acrylic acid derivative, methacrylonitrile, glycidyl methacrylate, citric acid. A carbon fiber manufacturing method using lyocell fibers, characterized in that at least one selected from the group consisting of epichlorohydrin, polyethylimine, and glutaraldehyde.
라이오셀, 레이온계, 면직물, 키토산을 포함하는 군으로부터 선택되는 1종 이상인 것을 특징으로 하는 셀룰로오스 섬유나 셀룰로오스 유도체 섬유를 특징으로 하는 라이오셀 섬유를 이용한 탄소섬유 제조방법.
The method of claim 1,
Lyocell, rayon-based, cotton fabric, carbon fiber manufacturing method using lyocell fiber, characterized in that at least one selected from the group consisting of chitosan or cellulose fiber or cellulose derivative fiber.
상기 단계 S2의 방사선은 감마선, 전자선, 이온빔, 중성자 빔, 자외선 및 X선으로 이루어진 군으로부터 선택되는 것을 특징으로 하는 라이오셀 섬유를 이용한 탄소섬유 제조방법.
The method of claim 1,
The radiation of step S2 is a carbon fiber manufacturing method using lyocell fibers, characterized in that selected from the group consisting of gamma rays, electron beams, ion beams, neutron beams, ultraviolet rays and X-rays.
상기 단계 S2의 방사선 총 조사량은 50~500 kGy 인 것을 특징으로 하는 라이오셀 섬유를 이용한 탄소섬유 제조방법.
The method of claim 1,
The carbon fiber manufacturing method using the lyocell fiber, characterized in that the total radiation dose of the step S2 is 50 ~ 500 kGy.
상기 단계 S1에서 열에 의해서 그라프트화 하는 것은 80 ℃이상에서 가열하는 것을 특징으로 하는 라이오셀 섬유를 이용한 탄소섬유 제조방법.
The method of claim 1,
Grafting by heat in the step S1 is a carbon fiber manufacturing method using lyocell fibers, characterized in that heating at 80 ℃ or more.
상기 단계 S3의 건조는 열건조, 자연건조 및 동결 건조로 이루어지는 군으로부터 선택되는 어느 하나인 것을 특징으로 하는 라이오셀 섬유를 이용한 탄소섬유 제조방법.
The method of claim 1,
The drying of step S3 is a carbon fiber manufacturing method using lyocell fibers, characterized in that any one selected from the group consisting of heat drying, natural drying and freeze drying.
The method according to claim 1, wherein the heat treatment temperature increase rate in step 2 is 1 to 10 °C per minute and is performed at 200 to 300 °C for 30 minutes to 3 hours.
상기 단계 S5의 탄화는 승온속도를 1~10℃/min 으로 하여 500~2500 ℃에서 진행되는 것을 특징으로 하는 라이오셀 섬유를 이용한 탄소섬유 제조방법.
The method of claim 1,
The carbonization of step S5 is a carbon fiber manufacturing method using lyocell fiber, characterized in that it proceeds at 500 ~ 2500 ℃ with a temperature increase rate of 1 ~ 10 ℃ / min.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020210040200A KR102480304B1 (en) | 2021-03-29 | 2021-03-29 | A Manufacturing method of carbon fibers from lyocell fiber |
| KR1020220174328A KR102662920B1 (en) | 2021-03-29 | 2022-12-14 | A manufacturing method of carbon fibers from cellulose fiber or cellulose derivative fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020210040200A KR102480304B1 (en) | 2021-03-29 | 2021-03-29 | A Manufacturing method of carbon fibers from lyocell fiber |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020220174328A Division KR102662920B1 (en) | 2021-03-29 | 2022-12-14 | A manufacturing method of carbon fibers from cellulose fiber or cellulose derivative fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20220134922A true KR20220134922A (en) | 2022-10-06 |
| KR102480304B1 KR102480304B1 (en) | 2022-12-21 |
Family
ID=83597059
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020210040200A KR102480304B1 (en) | 2021-03-29 | 2021-03-29 | A Manufacturing method of carbon fibers from lyocell fiber |
| KR1020220174328A KR102662920B1 (en) | 2021-03-29 | 2022-12-14 | A manufacturing method of carbon fibers from cellulose fiber or cellulose derivative fiber |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020220174328A KR102662920B1 (en) | 2021-03-29 | 2022-12-14 | A manufacturing method of carbon fibers from cellulose fiber or cellulose derivative fiber |
Country Status (1)
| Country | Link |
|---|---|
| KR (2) | KR102480304B1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102480304B1 (en) * | 2021-03-29 | 2022-12-21 | 전주대학교 산학협력단 | A Manufacturing method of carbon fibers from lyocell fiber |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090025974A (en) * | 2007-09-07 | 2009-03-11 | 주식회사 코오롱 | Cellulose-based composition fiber, tire cord, and spinning oil |
| KR20100113125A (en) * | 2008-02-15 | 2010-10-20 | 플레이텍스 프로덕츠, 엘엘씨. | Tampon including crosslinked cellulose fibers and improved synthesis processes for producing same |
| KR20100121386A (en) * | 2009-05-08 | 2010-11-17 | 국방과학연구소 | Method for manufacturing lyocell based carbon fiber and lyocell based carbon fabric |
| KR20140048362A (en) * | 2012-10-08 | 2014-04-24 | 한국원자력연구원 | Radiation biomolecules bacterial cellulose nanofibers and method of manufacture |
| KR101451384B1 (en) * | 2013-09-17 | 2014-10-22 | 한국과학기술연구원 | Method of preparing carbon fiber from wood waste including adhesive |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09143824A (en) * | 1995-11-21 | 1997-06-03 | Toray Ind Inc | Carbon fiber, its precursor and their production |
| KR102480304B1 (en) * | 2021-03-29 | 2022-12-21 | 전주대학교 산학협력단 | A Manufacturing method of carbon fibers from lyocell fiber |
-
2021
- 2021-03-29 KR KR1020210040200A patent/KR102480304B1/en active IP Right Grant
-
2022
- 2022-12-14 KR KR1020220174328A patent/KR102662920B1/en active IP Right Grant
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090025974A (en) * | 2007-09-07 | 2009-03-11 | 주식회사 코오롱 | Cellulose-based composition fiber, tire cord, and spinning oil |
| KR20100113125A (en) * | 2008-02-15 | 2010-10-20 | 플레이텍스 프로덕츠, 엘엘씨. | Tampon including crosslinked cellulose fibers and improved synthesis processes for producing same |
| KR20100121386A (en) * | 2009-05-08 | 2010-11-17 | 국방과학연구소 | Method for manufacturing lyocell based carbon fiber and lyocell based carbon fabric |
| KR101138291B1 (en) | 2009-05-08 | 2012-04-24 | 국방과학연구소 | Method for manufacturing Lyocell based carbon fiber and Lyocell based carbon fabric |
| KR20140048362A (en) * | 2012-10-08 | 2014-04-24 | 한국원자력연구원 | Radiation biomolecules bacterial cellulose nanofibers and method of manufacture |
| KR101451384B1 (en) * | 2013-09-17 | 2014-10-22 | 한국과학기술연구원 | Method of preparing carbon fiber from wood waste including adhesive |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20230002184A (en) | 2023-01-05 |
| KR102662920B1 (en) | 2024-05-03 |
| KR102480304B1 (en) | 2022-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kim et al. | High-yield carbonization of cellulose by sulfuric acid impregnation | |
| US20100285223A1 (en) | Method for Manufacturing Lyocell Based Carbon Fiber and Lyocell Based Carbon Fabric | |
| JP6050762B2 (en) | Method for producing lignin fiber | |
| Wu et al. | A new cellulose based carbon fiber from a lyocell precursor | |
| EP2857355B1 (en) | Method for producing carbon material using catalyst, and carbon material | |
| KR102243001B1 (en) | Activated Carbon Fiber and Method for Preparing the Same | |
| KR101138291B1 (en) | Method for manufacturing Lyocell based carbon fiber and Lyocell based carbon fabric | |
| KR102662920B1 (en) | A manufacturing method of carbon fibers from cellulose fiber or cellulose derivative fiber | |
| CN110714352B (en) | Preparation method of self-supporting porous carbon fiber network material | |
| KR101300162B1 (en) | Natural fiber-based carbonaceous adsorbent and methode of manufacturing the same | |
| JP2002038334A (en) | Method for producing fine activated carbon fiber and fine activated carbon fiber produced thereby | |
| JP6604118B2 (en) | Method for producing carbon fiber sheet | |
| JP2016164313A (en) | Method for producing carbon fiber woven fabric and carbon fiber woven fabric | |
| JP2020117824A (en) | Active carbon fiber material | |
| KR101285702B1 (en) | Fiber-reinforced composite material | |
| CN109735966B (en) | Method for preparing activated carbon fiber with hollow structure from wood fiber | |
| KR101716142B1 (en) | Insoluble lignin nanofiber and method for menufactruing the insoluble lignin nanofiber | |
| Salehi et al. | Preparation of activated carbon fabrics from cotton fabric precursor | |
| US3556712A (en) | Method of making flame-proof fibers | |
| Zou et al. | Effects of Different Pretreatments Combined with Steam Explosion on the Properties of Bamboo Fibers. | |
| JP2017101350A (en) | Manufacturing method of carbon material using cupra fiber material | |
| CN111575834B (en) | Carbon nanofiber based on natural fibrilia raw material and preparation method thereof | |
| KR102588215B1 (en) | Carbon molding product derived from lignin and manufacturing method thereof | |
| KR102651011B1 (en) | Method of preparing cellulose knit carbon fiber fabric, cellulose knit carbon fiber fabric, method of preparing graphitized fiber fabric and graphitized fiber fabric | |
| KR20230158939A (en) | A lyocell-based carbon fiber or textile manufacturing method using only radiation pretreatment without cross-linking agents or flame retardants treatment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| A107 | Divisional application of patent | ||
| GRNT | Written decision to grant |