「カーボンナノチューブの評価・分散方法」 材料科学の基礎 第3号

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1 3 Materials Science

2 1 1 h-kataura@aist.go.jp SWCNT SWCNT SWCNT SWCNT PERIPUTOS SWCNT SWCNT n,m n-m 3 K SWCNT SWCNT 2,3 Scanning Tunneling Microscope, STM 4,5 sp 2 SWCNT SWCNT SWCNT ITO 1 SWCNT (8,3)-SWCNT Single-Wall Carbon Nanotube, SWCNT 1993 Iijima 1 SWCNT SWCNT SWCNT SWCNT 1 SWCNT 1 8,3 SWCNT SWCNT K K 1-2 SWCNT SWCNT Iijima SWCNT Ni Y SWCNT 6 SWCNT SWCNT 1200 SWCNT 7 SWCNT SWCNT 2 Tel: Fax: sialjpts@sial.com

3 SWCNT Chemical Vapor Deposition, CVD 2 CVD SWCNT HiPco 8 CoMoCAT 9 SWCNT CVD Maruyama SWCNT 10 Hata SWCNT SWCNT CVD SWCNT 1 /g 30 /g SWCNT SWCNT SWCNT SWCNT SWCNT SWCNT SWCNT Scanning Electron Microscope, SEM 2 SWCNT SWCNT SWCNT 2 1 SWCNT 1 SWCNT SWCNT SWCNT SWCNT Fe Ni Co Mo Y SWCNT sp 2 SWCNT SWCNT SWCNT SWCNT SWCNT SWCNT Multi-Wall Carbon Nanotube, MWCNT MWCNT MWCNT SWCNT SWCNT MWCNT 2 SWCNT 2 SWCNT SEM SWCNT Tel: Fax: safcjp@sial.com 3

4 2-1 SWCNT SWCNT SEM Transmission Electron Microscope, TEM SEM μm SWCNT SEM SWCNT SWCNT SWCNT TGA TEM SEM 1 SWCNT SWCNT TEM TEM 12 SEM TEM 2-2 Thermogravimetric Analysis, TGA SWCNT CO 2 3 SWCNT TGA SWCNT SWCNT SWCNT SWCNT 3 SWCNT 2-3 SWCNT 1 van Hove 1 SWCNT SWCNT SWCNT 4 Tel: Fax: sialjpts@sial.com

5 1.0 nm SWCNT 1100 nm SWCNT 1 E 11 s 700 nm E 22 s SWCNT 500 nm 1 E 11 M E 33 s E 44 s E 22 M SWCNT SWCNT SWCNT SWCNT E 22 S E 11 S SWCNT SWCNT 14 E 11 S E 11 S SWCNT SWCNT E 22 S 2 5 SWCNT 15 SWCNT SWCNT 2-4 SWCNT 6 CVD SWCNT 633 nm He-Ne cm -1 Radial Breathing Mode RBM RBM RBM RBM SWCNT SWCNT RBM SWCNT SWCNT 10% D nm =248 / ω R cm -1 D SWCNT ω R RBM 5 SWCNT SWCNT 6 CVD SWCNT 633nm Tel: Fax: safcjp@sial.com 5

6 1593 cm -1 G G Graphite sp 2 SWCNT SWCNT G SWCNT cm -1 sp 2 Defect D SWCNT SWCNT D SWCNT D G D SWCNT SWCNT nm He-Ne RBM 1.0 nm 1.0 nm SWCNT 633 nm E 22 S 6 SWCNT SWCNT 7 SWCNT 488 nm Ar nm E 11 M SWCNT SWCNT G SWCNT LO G Breit-Wigner-Fano BWF SWCNT G SWCNT SWCNT 7 CVD SWCNT 488nm 3 SWCNT PERIPUTOS 3-1 SWCNT TGA SWCNT SWCNT 2 1 SWCNT SWCNT PERIPUTOS SWCNT PERIPUTOS 16 PERIPUTOS "Purity Evaluated by Raman Intensity of Pristine and 6 Tel: Fax: sialjpts@sial.com

7 Ultracentrifuged Topping Of Single-wall carbon nanotubes" PERIPUTOS SWCNT G SWCNT SWCNT SWCNT G SWCNT SWCNT 100 SWCNT SWCNT SWCNT SWCNT SWCNT 17 SWCNT 100% 100% 100% SWCNT SWCNT SWCNT 50 mg 2 wt.% Sodium Cholate SC 50 ml 30 1/2 20 W/cm 2 SWCNT G 10min SWCNT SWCNT Pristine-SWCNT Pristine-SWCNT G 15min 40 % 40 % 3 SWCNT SWCNT 2 wt.% SC 1 SWCNT 100 % 100%-SWCNT 100%-SWCNT SEM SEM SWCNT 7 HiPco 2 SWCNT SWCNT SEM SWCNT SWCNT SWCNT SWCNT SWCNT RBM 8 Pristine-SWCNT 100%-SWCNT SWCNT Tel: Fax: safcjp@sial.com 7

8 CCD Pristine- SWCNT 100%-SWCNT SC SWCNT HiPco SWCNT SWCNT SWCNT SC 0%-SWCNT 100%-SWCNT SWCNT 11 SWCNT 10 SWCNT SWCNT G SWCNT 10 mw CCD 11 SWCNT 0% 100% 633nm 8 Tel: Fax: sialjpts@sial.com

9 0 % 13 G 0 % 100 % G 0 % 0 SWCNT Pristine-SWCNT 13 Pristine-SWCNT G PERIPUTOS 58 % 12 SWCNT 633nm nm SWCNT SWCNT 488 nm SWCNT Pristine-SWCNT G 14 SWCNT SWCNT S/N G SWCNT Pristine-SWCNT PERIPUTOS 58 % SWCNT G SWCNT SWCNT SWCNT 0 % SWCNT 12 PERIPUTOS SWCNT TGA SWCNT TGA Pristine-SWCNT 100%-SWCNT G I CNT I 100 Pristine-SWCNT PERIPUTOS P CNT P CNT = I CNT / I 100 TGA W M SWCNT W CNT W CNT = P CNT 1-W M SWCNT 40 % 29 % 31 % G SWCNT Tel: Fax: safcjp@sial.com 9

10 4 SWCNT SWCNT SWCNT TGA SWCNT SWCNT SWCNT SWCNT 5 1 S. Iijima; T. Ichihashi, Nature, 1993, 363, R. Saito; M. Fujita; G. Dresselhaus; M. S Dresselhaus, App. Phys. Lett., 1992, 60, N. Hamada; S. Sawada; A. Oshiyama, Phys. Rev. Lett., 1992, 68, J. W. G. Wildoer; L. C. Venema; A. G. Rinzler; R. E. Smalley; C. Dekker, Nature, 1998, 391, T. W. Odom; J.-L. Huang; P. Kim; C. M. Lieber, Nature, 1998, 391, C. Journet; W. K. Maser; P. Bernier; A. Loiseau; M. L. Chapelle; S. Lefrant; P. Deniard; R. Leek & J. E. Fischer, Nature, 1997, 388, A. Thess; R. Lee; P. Nikolaev; H. Dai; P. Petit; J. Robert; C. Xu; Y. H. Lee; S. G. Kim; A. G. Rinzler; D. T. Colbert; G. E. Scuseria; D. Tomanek; J. E. Fischer; R. E. Smalley, Science, 1996, 273, P. Nikolaev; M. J. Bronikowski; R. K. Bradley; F. Rohmund; D. T. Colbert; K. A. Smith; R. E. Smalley, Chem. Phys. Lett., 1999, 313, S. M. Bachilo; L. Balzano; J. E. Herrera; F. Pompeo; D. E. Resasco; R. B. Weisman, J. Am. Chem. Soc., 2003, 125, S. Maruyama; R. Kojima; Y. Miyauchi; S. Chiashi; M. Kohno, Chem. Phys. Lett., 2002, 360, K. Hata; D. N. Futaba; K. Mizuno; T. Namai; M. Yumura; S. Iijima, Science, 2004, 306, Y. Sato; K. Yanagi; Y. Miyata; K. Suenaga; H. Kataura; S. Iijima, Nano Lett., 2008, 8, H. Kataura; Y. Kumazawa; Y. Maniwa; I. Umezu; S. Suzuki; Y. Ohtsuka; Y. Achiba, Synth. Met., 1999, 103, M. J. O Connell; S. M. Bachilo; C. B. Huffman; V. C. Moore; M. S. Strano; E. H. Haroz; K. L. Rialon; P. J. Boul; W. H. Noon; C. Kittrell; J. Ma; R. H. Hauge; R. B. Weisman; R. E. Smalley, Science, 2002, 297, S. M. Bachilo; M. S. Strano; C. Kittrell; R. H. Hauge; R. E. Smalley; R. B. Weisman, Science, 2002, 298, D. Nishide; Y. Miyata; K. Yanagi; T. Tanaka; H. Kataura, Phys. Status Solidi B, 2009, 246, D. Nishide; Y. Miyata; K. Yanagi; T. Tanaka; H. Kataura, Jpn. J. App. Phys., 2009, 48, nm 488nm G 10 Tel: Fax: sialjpts@sial.com

11 CoMoCAT SouthWest NanoTechnologies SWeNT SouthWest NanoTechnologies P2B Q T1% TGA Web Material Matters Vol.4 No.1 Carbon nanotube, single-walled SWeNT CG-100 >90% carbon 65% carbon as SWCNT, T1% nm mode: 800nm; AFM nm AFM Carbon nanotube, single-walled SWeNT CG-200 >90% carbon 77% carbon as SWCNT, T1% nm MWCNT DWCNT Carbon nanotube, single-walled, 6,5 chirality SWeNT SG-65 >90% carbon 77% carbon as SWCNT, T1% >50% 6, nm mode: 900nm; AFM nm AFM Carbon nanotube, single-walled, 7,6 chirality SWeNT SG-76 >90% carbon 77% carbon as SWCNT, T1% >50% 7, nm mode: 800nm; AFM nm AFM MG, 1G MG, 1G MG, 1G MG, 1G SWeNT 1 PERIPUTOS SWCNT CG % CG % SG-65 61% SG-76 81% T1% PERIPUTOS Carbon nanotube, single-walled, octadecylamine functionalized % carbon basis wt.% ODA 4 % metals 2 10 nm µm bundles THF, 1,2-Dichlorobenzene, CS 2 1 mg/ml MG 2, 3 Carbon nanotube, single-walled, polyaminobenzene sulfonic acid functionalized MG % carbon basis 65 % PABS, typical 4 % metals 4 5 nm µm bundles Mw g/mol PABS H 2 O = 5.0 mg/ml, DMF = 0.1 mg/ml, Ethanol = 0.05 mg/ml Carbon nanotube, single-walled, poly ethylene glycol functionalized 2 > 80 % carbon basis PEG:SWNT: 20: % metals 4 5 nm µm bundles Mw 600 g/mol PEG H 2 O = 5.0 mg/ml MG Carbon nanotube, single-walled, amide functionalized > 90 % carbon basis 4 atom% amide groups 5-8 % metals 4 6 nm µm bundles DMF: mg/ml with sonication acetone, alcohols: mg/ml with sonication MG Carbon nanotube, single-walled, carboxylic acid functionalized 1 SWNT > 90 % carbon basis atom% carboxylic acid 5-8 % metals 4 5 nm µm bundles DMF = 1.0 mg/ml, H 2 O = 0.1 mg/ml MG 1G Reference 1 Niyogi, S. et al. Accts. Chem. Res. 2002, 35, Zhao, B. et al. J. Am. Chem. Soc. 2005, 127, Zhao, B. et al. Adv. Funct. Mater. 2004, 14 1, 71. Tel: Fax: safcjp@sial.com 11

12 1 2 1 uchida-kunio@aist.go.jp 2 s-endoh@aist.go.jp TEM MWCNT 10 nm nm MWCNT MWCNT 450 nm MWCNT 2 3 MWCNT C MWCNT 1 MWCNT MWCNT 1a 1b 0.1 % 2 1a SEM 1b MWCNT SEM 2 MWCNT SEM CNT CNT NEDO 2000 CVD MWCNT CVD NEDO CVD MWCNT CVD MWCNT 2000 MWCNT 3a MWCNT 20 μm 12 Tel: Fax: sialjpts@sial.com

13 ml 30 g ml a CVD WCNT TEM 3b CVD MWCNT TEM MWCNT 30 nm MWCNT 3b MWCNT MWCNT MWCNT 4 MWCNT MWCNT MWCNT MWCNT 2.0 g 50 ml 20 mm 540 g 90 cm ml MONO P-6 FRITSCH 450 rpm / = 9/ mm MWCNT 500 ml 300 ml MWCNT 2 mm 0.2 ml 20 mm 540 g 250 ml 450 rpm ml MWCNT 5 mm ml μm 300 ml % 7 6 MWCNT ml 5 ml 100 ml μm Tel: Fax: safcjp@sial.com 13

14 2-5 Triton X mg/ml 900 ml Bronson 450W 30 MWCNT H-9R 3000G 3000G 3 TEM 8 MWCNT 3000G 20000G 20000G G MWCNT TEM 9a 5 μm MWCNT TEM 9b MWCNT TEM 20000G MWCNT 2-6 MWCNT CNT 0.5 mg/ml Triton-X mg/ml MWCNT 10 ml MWCNT MWCNT 0.5 mg/ ml Triton-X100 CNT 1 mg/ml CNT 1 mg/ml 4 12 UPA G TEM 12 MWCNT 3-2 TEM 9a MWCNT TEM 9b MWCNT TEM 1 CNT 100 TEM MWCNT G TEM 13 MWCNT TEM 14 Tel: Fax: sialjpts@sial.com

15 4 MWCNT MWCNT 6 MWCNT NEDO 4 14 MWCNT NEDO S. Iijima Nature, 1991, 354, U.S. Pat. No.5, 1996, 560, , 1995, , Y. Morimoto et al. "Deposition and biopersistence of inhaled MWCNT in rat lung". Nanotoxicology 2010, Edinburgh, UK. 6 T. Seto et al. Aerosol Sci. and Technol., 2010, 44, Carbon nanotube, multi-walled, bundled SWeNT SMW 100 >95% carbon content 6-9 nm 5 μm 3 6 CoMoCAT Carbon nanotube, multi-walled Graphistrength C100 Carbon nanotube, multi-walled Carbon nanotube, multi-walled >90% carbon content trace metal basis nm 2-6 nm μm 5 15 ICP TEM CVD >99% carbon content (trace metal basis) 6-13 nm μm ( 7 13 ) BET 220 m 2 /g (SSA) CVD ( ) >90% carbon content 0.1 % (Fe) nm 5 9 μm CVD Carbon nanotube array, multi-walled vertically aligned on silicon wafer substrate Carbon nanotube array, multi-walled vertically aligned on copper wafer substrate Carbon content, >99.9% structured sp 2 carbon. <0.1% amorphous sp 3 carbon. CNT 100 nm 10 nm 30 μm 3 μm 2 x 109 MWCNT/cm 2 20 tubes / μm 2 CVD PECVD 1cm 1cm, {100}, μm thick, low n-doped phosphorus, resistivity 1-30 Ω cm. 1cm 1cm 0.05cm high conductivity low-oxygen G, 100G G, 25G G G, 10G EA EA Vacuum Release CNT MWCNT SEM SEM 10 μm Tel: Fax: safcjp@sial.com 15

16 Aldrich URL Material Matters sialjp@sial.com CoMoCAT and SWeNT are registered trademarks of SouthWest NanoTechnologies, Inc. Graphistrength is a registered trademark of Arkema Inc. Sigma, Aldrich and Sigma- Aldrich are registered trademarks of Sigma-Aldrich Biotechnology LP and Sigma-Aldrich Co.. Vacuum Release is a trademark of Gel-Pak. Material Matters is a trademark of Sigma-Aldrich Biotechnology LP and Sigma-Aldrich Co..

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