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1 ISSN(Print) ISSN(Online) X Textile Coloration and Finishing Vol.26,No.2 Reviews 카본나노튜브를이용한고성능나노복합재료의개발동향 이민경배수빈박종규이승걸 1, 국방과학연구소 4본부 3부, 1 부산대학교유기소재시스템공학과 The Development of High Performance Nano-composites with Carbon Nanotube Min-Kyung Lee, Soo Bin Bae, Jong Kyoo Park and Seung Geol Lee 1, The 4 th R&D Institute-3, Agency for Defense Development, Daejeon, Korea 1 Department of Organic Material Science and Engineering, Pusan National University, Busan, Korea (Received: May 16, 2014 / Revised: May 30, 2014 / Accepted: May 31, 2014) Abstract: This review paper is a state of the art report of the development of high performance nano-composites with carbon nanotube. We investigate the research and development (R&D) trends of high performance nano-composites with carbon nanotube by analyzing technical trends in research institutes and industry. We report the R&D and technology trends for the properties and applications of fabrication of hybrid composites with aligned carbon nanotubes, multifunctional fiber/carbon nanotube composites. We discuss the specific topics including unidirectional carbon nanotube, carbon nanotube forests, transfer-printing carbon nanotube technology, deposition of carbon nanotube by electrophoresis, vapor grown carbon fiber (VGCF), cup-stacked carbon nanotube, bucky paper and carbon nanotube yarns in this review paper. Keywords: composites, carbon nanotube, carbon fiber, nano-composites, high performance 1. 서론 최근다양한분야의첨단기술이발전하고있어, 그에따른새로운소재에대한필요성이점점증가하고있다. 그중연료효율증대및이산화탄소등과같은지구온난화가스배출의절감을위한환경보호와관련된기술이나날이발전하고있다. 특히자동차, 철도, 선박, 우주 항공등의운송수단에사용되는소재는철강, 알루미늄등의금속소재가주를이루어왔으나, 최근에는경량화및우수한기계적특성, 다양한기능화부여등이가능한복합재료가운송용소재로활발하게적용되고있다 1). 연료효율증대와지구온난화가스배출의절감은상기와같은운송수단에적용되는소재에따라크게영향을받기때문에, 복합재료가기존의금속소재를대체하기위한대안으로제시되고있다. 복합재료에서가장핵심적인소재가탄소섬유 Corresponding author: Seung Geol Lee (seunggeol.lee@pusan.ac.kr) Tel.: Fax.: c2014 KSDF /2014-6/71-78 인데, 탄소섬유는고강도, 고탄성을구현하고동시에무게가가볍고, 내열성, 내충격성, 내화학약품성등이뛰어나운송분야뿐만아니라다양한분야로사용범위가확대되고있다. 특히고성능탄소섬유는인장강도, 탄성률이매우크고, 내마모성, 윤활성, 전도성이우수하여우주 항공용 1차구조재료로사용하는등고부가가치산업에있어핵심이되는소재이므로기술유출에민감하여자국외의수출을규제하고있어우주 항공산업, 군수산업등고부가가치산업의발전을위해고성능탄소섬유는반드시개발되어야할과제이다. 고성능복합재료의개발과더불어탄소나노튜브 (carbon nanotube, CNT) 등의나노소재를이용한나노기술은전자정보통신, 에너지, 바이오등의분야에서필수적인기술로소재분야뿐만아니라다양한분야에서응용가능성이높다 2). 최근고성능복합재료의개발에상기와같은나노소재를활용하여기계적물성및열적 전기적물성등을강화하려는연구가활발히진행되고있고미국등선진 71

2 72 이민경배수빈박종규이승걸 국에서는군사적용도로제품화단계까지개발이이루어지고있다. 하지만현재국내에서는우주 항공산업용및군사용목적의고성능복합재료의핵심소재및원천기술은대부분수입에의존하고있어해외의존도가매우높은실정이다. 이러한신소재분야의원천기술은단기간에개발하기어렵고대규모투자가필요하며개발실패등의높은위험이따르기때문에정부차원의관심과지원이필요하다고사료된다. 따라서, 본고에서는고성능복합재료의개발을위한탄소나노튜브의응용에대한연구동향을분석하고자한다. 2. 탄소나노튜브복합재료의연구개발동향 Iijima 박사가 1991년에최초로발견 3) 한탄소나노튜브는뛰어난기계적, 열적, 전기적특성을가지고있어복합재료의이상적인충전재로서사용될수있다. 초기에는탄소나노튜브의분산및매트릭스간접착의어려움으로인해기계적물성향상보다는전기적 열적특성등기타물성에초점을둔연구가진행되었으나, 최근에는초고강도 초경량복합재료분야등에서탄소나노튜브를충전재로사용하여복합재료의내열성, 난연성, 내마모성, 내충격성, 내침성등다기능성을향상시키는데주요연구를수행하고있고, 다양한응용연구도활발히진행중이다. 탄소나노튜브의뛰어난기계적특성이복합재료에서효과적으로발현되기위해서는반드시고분자매트릭스내에서의탄소나노튜브의높은분산도가확보되어야한다. 그러나탄소나노튜브표면의결합에너지때문에다발형태로쉽게응집되어, 이로인한복합재료내부의응력집중현상으로기계적물성이저하되는단점이있다. 따라서탄소나노튜브의복합화를위한연구는대부분복합재료내의탄소나노튜브의분산성을향상시키는것에초점이맞추어져있으며, 여러가지다양한접근법을통해기계적물성향상을위한연구를진행하고있다. 국내의경우탄소나노튜브복합재료관련연구는 LG화학, 한화, 효성, 제일모직등에서연구되고있으며, 선진국에비해기초연구및특성평가등에서는뒤쳐져있지만응용제품개발에서는유사한수준까지발전한것으로판단된다 4,5). 국내연구기관에서는탄소나노튜브의분산특성연구 6,7) 와슈퍼소재와관련된연구 8,9) 를활발하게진행하고있지만, 탄소나노튜브를섬유강화복합재료에적용한연 구는국방과학연구소 (ADD), 재료연구소 (KIMS) 등몇몇기관에국한되어있고상용화한사례도아직미미하다. 따라서, 본고에서는탄소나노튜브를섬유강화복합재료에적용한기술개발사례를해외기관중심으로살펴보고자한다. 2.1 섬유 / 탄소나노튜브의복합화기술 섬유상탄소나노튜브성장 Ci 연구팀은탄소나노튜브를랜덤 (random) 한방향으로수지에분산하는기존의나노복합재료제작방식과달리, 탄소섬유에탄소나노튜브를일정한방향으로성장시켜복합재료에적용하는기술을처음으로연구하였다 10). 섬유표면에탄소나노튜브를수직으로성장시킨복합재료는순수레진에비하여축방향강성 (Figure 1(a)) 과감쇠성능 (Figure 1(b)) 이각각 3300%, 2100% 향상되었으며, 동일한비율의탄소나노튜브를수지에무배향으로분산시킨경우와비교하여약 3배이상의강화효과를얻었다. Thostenson 연구팀은처음으로화학기상증착법을이용하여탄소섬유표면에탄소나노튜브를성장시켰다 11). Figure 2에서보는바와같이 Thostenson 연구팀은탄소나노튜브를접목한탄소섬유의단섬유파괴시험에서섬유와매스릭스 ( 수지 ) 의계면특성을관찰한결과, 계면전단강도가약 15% 향상되었다고보고하였다. 이는탄소나노튜브와매트릭스물질과의상호작용으로인해하중전달이증가되었기때문으로사료된다. 또한응력에따라생기는복굴절패턴으로부터섬유표면에성장된탄소나노튜브가계면접착력을향상시킴을관찰할수있다. Thostenson 연구팀에서제시한방법은탄소나노튜브와탄소섬유를접목한복합재료의개발을한층더성장시키는계기를마련하였다 탄소나노튜브숲섬유강화복합재료적층기술미국하와이대학 N. Ghasemi-Nejhad 연구팀은탄소나노튜브숲 (carbon nanotube forests) 을이용한 3D 복합재료를개발하였다 12). 기본개념구조는 Figure 3에서보는바와같이탄소나노튜브숲을직물복합재료층에수직방향으로보강하여기존의적층형직물복합재료의층간분리파손단점을보완한복합재료이다. 탄소나노튜브숲으로보강된복합재료는기계적특성이향상되었으며, 기존의적층형직물복합재료와비교 한국염색가공학회지제 26 권제 2 호

3 카본나노튜브를이용한고성능나노복합재료의개발동향 73 Figure 1. (a) Compressive stress-strain characterization, (b) Dissipated energy per unit volume during compressive cycles 10). Figure 2. SEM image of carbon fibers (a) before and (b) after nanotube growth, and (c) TEM image of the nanocomposite structure near the fiber/matrix interface. Results of the single-fiber fragmentation tests (d) and birefringence patterns (e) 11). Textile Coloration and Finishing(J. Korean Soc. Dye. and Finish.), Vol. 26, No. 2

4 74 이민경배수빈박종규이승걸 Figure 4. Transfer-printing CNT to prepreg: (a) Scheme of the transfer-printing process, (b) CNT forest on the prepreg ply, (c, d) SEM image of the CNT forest 13). Figure 3. Scheme of the steps for manufacturing of a 3D composite: (1) Aligned nanotubes grown on the fabric, (2) Stacking, (3) Fabrication 12). 하여층간인장파괴인성값 4.5배, 층간전단강도 1.55배, 감쇠성능 6.15배향상, 두께방향열팽창계수 60% 감소등기존직물복합재료의층간분리문제를보완하였다 전사공정을이용한탄소나노튜브수직배열 MIT의 A. John Hart 연구팀은고분자매트릭스내의탄소나노튜브분산의어려움으로계면접착력이감소하는것을방지하기위하여화학기상증착법을이용하여탄소나노튜브를수직으로정렬시키는방법을제안하였다 13). Figure 4에서보는바와같이실리콘기판위에수직으로성장된탄소나노튜브는일정한압력으로롤러를통하여프리프레그시트로전사된다. 프리프레그위에수직방향으로정렬된탄소나노튜브는층간계면접착력을증가시키므로기계적강도가향상되며, 탄소나노튜브의길이를조절할수있으므로이에따른물성변화도가능하다. 전사공정은탄소나노튜브표면의개질없이매트릭스에분산이가능하므로탄소나노튜브를손상시키지않아고유의물성을저하시키지않는반면, 공정시제작이어려워장시간이소요된다는단점이있다 전기영동법에의한적층기술 R. C. Haddon 연구팀은전기영동법을이용하여탄소섬유에탄소나노튜브를적층시키는방법을개발하였다 (Figure 5) 14). 이는기존의화학기상증착법으로성장된탄소섬유표면의사이징 (sizing) 처리문제를개선한방법으로탄소섬유의강도저하의우려가없어관련산업에적용이용이할것으로예상된다. 전기영동법을통하여제작된탄소나노튜브복합재료는 1 wt% 의다중벽탄소나노튜브적용시기존복합재료의물성을층간전단강도와전기전도도를각각 27%, 30% 향상시켰다. 면외방향 (out-of -plane) 에서의전기전도도는탄소나노튜브를적층한복합재료가상대적으로높게나타났다. 단일벽탄소나노튜브가적층된복합재료의면외방향측정값은 S/cm로기존의탄소섬유복합재료보다 2 Figure 5. (a) Scheme of deposition of CNTs on a carbon fiber surface by electrophoresis, (b, c) SEM image of carbon fibers with CNTs 14). 한국염색가공학회지제 26 권제 2 호

5 카본나노튜브를이용한고성능나노복합재료의개발동향 75 배향상된반면면내방향 (in-plane) 으로측정된전기전도도는뚜렷한영향이없는것으로나타났다. 2.2 섬유 / 탄소나노튜브의기능화응용기술 분말법을이용한기상성장탄소섬유 / 에폭시복합재료 기상성장탄소섬유분말 (vapor grown carbon fiber, VGCF) 은상대적으로가격이낮아대량생산이가능할뿐만아니라공정과정이간단하여기대되는충진재중의하나이다. Fukunaga 연구팀은탄소섬유분말을작은체를이용하여분산시킨후상부프리프레그에탄소섬유분말을작은체를이용하여분산시킨후상부프리프레그를적층시켜복합재료를제조하였다 (Figure 6) 15). 이때분산된탄소섬유분말밀도를 10, 20, 30g/m 3 으로각각변화시키면서기계적물성을측정하였다. Mode I 파괴인성결과는탄소섬유분말밀도가 20g/m 3 인경우에가장좋게나타났으며탄소섬유분말밀도가 30g/m 3 인경우는분말을첨가하지않는프리프레그보다오히려더낮은값을나타내었다. 이는중간층삽입시기계적물성향상에대한분말의최적혼합비가존재하기때문인것으로사료된다 컵케익탄소나노튜브 일본의 Enomoto 연구팀은탄소나노튜브가컵의형상으로적층되어섬유상이되는특이한형태를이용하면복합재료의강도및강성이향상되는것을발견하였다 16). Figure 7에서보는바와같이컵적층형태의탄소 나노튜브는탄소나노튜브표면에노출된 edge site 로불리는활성점에의해고분자매트릭스와의결합력이향상된다. 파괴인성실험결과에의하면컵케익탄소나노튜브를 5 wt% 첨가한복합재료는미첨가복합재료에비해파괴인성이 Mode I에서약 2배, Mode II에서약 1.3배향상되었다 버키페이퍼홍콩대학의연구팀은 Figure 8에서보는바와같이탄소섬유복합재료에에폭시수지를침투시킨탄소섬유버키페이퍼 (bucky paper) 를삽입층으로사용하여이를통해계면전단응력 31%, Mode II 파괴인성을 104% 향상시켰다 17). 기계적물성을높이기위하여탄소나노튜브등의충전재를혼합하게되면수지의점도가높아서분산성이떨어지므로이연구팀에서제안한시트 (sheet) 형태의삽입층기술은많은응용연구가가능할것으로예상된다. 연구팀은탄소섬유시트에에폭시수지를침투시키기위한방법으로소킹 (soaking), 열압축성형 (hot compression molding), 진공침투 (vacuum infiltration) 방법을사용하여복합재료를제작하였다. 소킹법으로제조된복합재료는매트리스에빈공간 (void) 이많아상대적으로탄성율이적게나타났으며진공침투법으로제작한복합재료의탄성율이가장좋게나타났다. 또한버키페이퍼삽입층을적용한경우계면전단강도와 Mode II 파괴인성값이증가하였는데, 층간파괴시험에서버키페이퍼를삽입한복합재료의층간파괴형태를관찰한결과, 지그재그 (zig-zag) 로균열이진행된것을관찰할수있었다. 이러한형태의균열은일직선으로생성되는균열에비하여상대적으로표면적이넓어균열전파에더많은구동력을요구하게되므로파괴인성이증가된다. 이와같이버키페이퍼삽입층기술은많은양의카본나노튜브를포함할수있어층간계면특성의 Figure 6. Scheme of powder method for dispersing VGCF on CFRP prepreg 15). Figure 7. (a) Scheme of cup-stacked carbon nanotube, (b) SEM image of cup-stacked carbon nanotube 16). Textile Coloration and Finishing(J. Korean Soc. Dye. and Finish.), Vol. 26, No. 2

6 76 이민경배수빈박종규이승걸 Figure 8. Scheme of a fabrication of CNF bucky papers 17). 향상을가져올뿐만아니라나노입자분산의문제점을해결할수있어상용화의가능성이높다. Figure 9에서보는바와같이실제로미국의 Nanocomp Technologies사에서대면적버키페이퍼를제조하여차세대전자파차폐, 대전방지용항공기및방탄소재로활용하고있다. 2.3 탄소나노튜브섬유중국칭화대학의 Shoushan Fan 연구팀은 Figure 10에서보는바와같이건식공정에의해제조된탄소나노튜브섬유를개발하였다 19). 탄소나노튜브가지니는반데르발스힘을이용하여탄소나노튜브가자발적으로섬유상을형성하도록하여약수십 cm 길이를갖는탄소나노튜브섬유를제조하였다. 같은시기에미국텍사스대학의 Baughman 연구팀은탄소나노튜브숲으로부터탄소나노튜브섬유를제작하였다 20). 또한 Baughman 연구팀은호주의 산업섬유기술연구소와공동으로투명하면서강도가우수한다중벽탄소나노튜브부직포형시트를제조하였다 21). 이시트는탄소나노튜브숲으로부터섬유를추출하는방법과유사하게시트를제조할수있으며유연성과전기전도성및내열성이우수하므로다양한분야에적용이가능하다 22). 건식공정을이용해순수탄소나노튜브섬유를제조하는연구가활발해짐에미국로스알라모스국립연구소의 Yuntian Zhu 연구팀은더욱개선된방법으로초고강도섬유를제조하였고, 이섬유는약 50GPa 정도의강도를지니며같은무게의강철에비해약 100배정도높은강도값을보인다고보고 Figure 9. Product of large bucky paper by Nanocomp Technologies 18). Figure 10. (a) Carbon nanotube yarns, (b, c) SEM images of carbon nanotube yarns, (d) SEM images of various types of carbon nanotube yarns 19,20). 한국염색가공학회지제 26 권제 2 호

7 카본나노튜브를이용한고성능나노복합재료의개발동향 77 Figure 11. Product of carbon nanotube yarns by Nanocomp Technologies 18). 하였다 23). 제조된섬유는이중벽탄소나노튜브를이용한경량의초고강도소재이기때문에향후우주항공분야, 수송기기, 방탄복, 스포츠분야등다양한분야에서적용이가능할것이라고예상된다. 최근에는 Figure 11에서보는바와같이미국의 Nanocomp Technologies사에서연속상의탄소나노튜브섬유를상업적으로생산할수있는기술을개발하였으며, 이섬유는강도가강철보다약 100배정도높고전기전도성과내열성이우수하여향후고성능경량섬유로각광받을것으로기대된다. 3. 결론 본연구조사에서는최근논문및기술동향분석을통하여나노소재를이용한나노복합재료의연구동향및개발방향을해외기관중심으로분석하였다. 탄소나노튜브는기계적, 열적, 전기적성질이뛰어나새로운형태의복합재료용충전재로서응용될수있는가능성이높다. 탄소나노튜브를이용한나노복합재료는미국등선진국에서특수목적으로개발되고있으며, 자동차뿐만아니라항공우주, 국방분야의고강도다기능소재등에활용될수있어방대한시장형성이예상된다. 그러나탄소나노튜브의가격과분산문제로인해충전재로첨가할수있는양의한계가있어그사용이제한적이며, 탄소나노튜브의분산기술은상업화의초기시장에서기술이전등이쉽지않다는문제도있다. 그리고탄소나노튜브및다른나노입자, 고분자등관련된재료의데이터베이스화도필요한것으로사료된다. 따라서이를해결하기위한여러가지방법들이동원되고있으며, 실용화를위한연구를진 행중이다. 탄소나노튜브시장은복합재료를중심으로성장이예상되나가격 (kg 당 $100 수준 ), 생산성등의문제로상업화가더디게진행되고있고, 그규모도소규모이다. 하지만, 뛰어난물성으로인해고부가가치소재로활용이가능하며미래형소재로서관심이지속되고있다. 따라서중 장기적으로가격및단일소재로서의적용성등의한계를극복하는것이관건이다. 또한상업적으로효용성이있는대량생산공정기술, 개질및분산기술, 복합재료의가공기술등의연구가함께필요한것으로사료되어탄소나노튜브의성장은화학, 소재산업의관점에서장기적설계와안목이필요하다. References 1.K. S. Kim, K. M. Bae, S. Y. Oh, and M. K. Seo, Trend of Carbon Fiber-reinforced Composites for Lightweight Vehicles, Elastomers and Composites, 47(1), 65(2012). 2. S. C. Lyu, J. H. Sok, and J. H. Han, Technical Trends of Carbon Nanotubes Growth Method, KIC News, 12(4), 1(2009). 3. S. Iijima, Helical Microtubules of Graphitic Carbon, Nature, 354(6348), 56(1991). 4. B. G. Min, R&D Trend of CNT/Polymer Nanocomposites, Polymer Science and Technology, 16(2), 176(2005). 5. D. S. So, I. Kang, K. H. Kim, B. K. Choi, and H. Ham, Application of Carbon Nanotube, Korean Industrial Chemistry News, 12(4), 28(2009). 6. J. H. Kim, H. Y. Ma, S. Y. Yang, and S. J. Kim, Analysis of Electrical and Physical Property of the PU/MWNT Film and Dispersion Characteristics of MWNT According to the Solvent, Textile Coloration and Finishing(J. of Korea Soc. Dyers and Finishers), 24(1), 69(2012). 7. H. Y. Ma, S. Y. Yang, and S. J. Kim, Analysis on ESD Properties of the PANI added PU/MWNT Films, Textile Coloration and Finishing(J. of Korea Soc. Dyers and Finishers), 25(1), 37(2013). 8. S. M. Park, I. J. Kwon, J. H. Sim, J. H. Lee, S. S. Kim, M. C. Lee, and J. S. Choi, Improving the Photo-stability of p-aramid Fiber by TiO 2 Textile Coloration and Finishing(J. Korean Soc. Dye. and Finish.), Vol. 26, No. 2

8 78 이민경배수빈박종규이승걸 Nanosol, Textile Coloration and Finishing(J. of Korea Soc. Dyers and Finishers), 25(2), 126(2013). 9. Y. I. Lee, M. H. Jung, and M. C. Lee, Improvement of Photo-stability for p-aramid Fibers by SiO 2/TiO 2 Sol-Gel Method, Textile Coloration and Finishing(J. of Korea Soc. Dyers and Finishers), 25(3), 172(2013). 10. L. Ci, J. Suhr, V. Pushparaj, X. Zhang, and P. M. Ajayan, Continuous Carbon Nanotube Reinforced Composites, Nano Letters, 8(9), 2762(2008). 11. E. T. Thostenson, W. Z. Li, D. Z. Wang, Z. F. Ren, and T. W. Chou, Carbon Nanotube/carbon Fiber Hybrid Multiscale Composites, J. of Applied Physics, 91(9), 6034(2002). 12. V. P. Veedu, A. Y. Cao, X. S. Li, K. G. Ma, C. Soldano, S. Kar, P. M. Ajayan, and M. N. G. Nejhad, Multifunctional Composites using Reinforced Laminae with Carbon-nanotube Forests, Nature Materials, 5(6), 457(2006). 13. E. J. Garcia, B. L. Wardle, and A. J. Hart, Joining Prepreg Composite Interfaces with Aligned Carbon Nanotubes, Composites Part a-applied Science and Manufacturing, 39(6), 1065(2008). 14. E. Bekyarova, E. T. Thostenson, A. Yu, H. Kim, J. Gao, J. Tang, H. T. Hahn, T. W. Chou, M. E. Itkis, and R. C. Haddon, Multiscale Carbon Nanotube-carbon Fiber Reinforcement for Advanced Epoxy Composites, Langmuir, 23(7), 3970(2007). 15. Y. Li, N. Hori, M. Arai, N. Hu, Y. L. Liu, and H. Fukunaga, Improvement of Interlaminar Mechanical Properties of CFRP Laminates using VGCF, Composites Part a-applied Science and Manufacturing, 40(12), 2004(2009). 16. T. Yokozeki, Y. Iwahori, S. Ishiwata, and K. Enomoto, Mechanical Properties of CFRP Laminates Manufactured from Unidirectional Prepregs using CSCNT-dispersed Epoxy, Composites Part a-applied Science and Manufacturing, 38(10), 2121(2007). 17. S. U. Khan and J. K. Kim, Improved Interlaminar Shear Properties of Multiscale Carbon Fiber Composites with Bucky Paper Interleaves made from Carbon Nanofibers, Carbon, 50(14), 5265(2012). 18. Q. W. Li, Y. Li, X. F. Zhang, S. B. Chikkannanavar, Y. H. Zhao, A. M. Dangelewicz, L. X. Zheng, S. K. Doorn, Q. X. Jia, D. E. Peterson, P. N. Arendt, and Y. T. Zhu, Structuredependent Electrical Properties of Carbon Nanotube Fibers, Adv. Mater., 19(20), 3358(2007). 19. K. L. Jiang, Q. Q. Li, and S. S. Fan, Nanotechnology Spinning Continuous Carbon Nanotube Yarns -Carbon Nanotubes Weave their Way into a Range of Imaginative Macroscopic Applications, Nature, 419(6909), 801(2002). 20. M. Zhang, K. R. Atkinson, and R. H. Baughman, Multifunctional Carbon Nanotube Yarns by Downsizing an Ancient Technology, Science, 306(5700), 1358(2004). 21. M. D. Lima, S. L. Fang, X. Lepro, C. Lewis, R. O. Robles, J. C. Gonzalez, E. C. Martinez, M. E. Kozlov, J. Y. Oh, N. Rawat, C. S. Haines, M. H. Haque, V. Aare, S. Stoughton, A. A. Zakhidov, and R. H. Baughman, Biscrolling Nanotube Sheets and Functional Guests into Yarns, Science, 331(6013), 51(2011). 22. K. R. Atkinson, S. C. Hawkins, C. Huynh, C. Skourtis, J. Dai, M. Zhang, S. L. Fang, A. A. Zakhidov, S. B. Lee, A. E. Aliev, C. D. Williams, and R. H. Baughman, Multifunctional Carbon Nanotube Yarns and Transparent Sheets: Fabrication, Properties, and Applications, Physica B, 394(2), 339(2007). 23. X. F. Zhang, Q. W. Li, T. G. Holesinger, P. N. Arendt, J. Y. Huang, P. D. Kirven, T. G. Clapp, R. F. D. Paula, X. Z. Liao, Y. H. Zhao, L. X. Zheng, D. E. Peterson, and Y. T. Zhu, Ultrastrong, Stiff and Lightweight Carbon-nanotube Fibers, Adv. Mater., 19(23), 4198(2007). 한국염색가공학회지제 26 권제 2 호

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