Table Of ContentPERSPECTIVES OF FULLERENE NANOTECHNOLOGY
Perspectives of Fullerene
Nanotechnology
Edited by
Eiji Osawa
Nanocarbon Research Institute, Chiba, Japan
"~.
KLUWER ACADEMIC PUBLISHERS
DORDRECHT/BOSTON/LONDON
Library of Congress Cataloging-in-Publication Data is available
ISBN 978-94-010-9600-3 ISBN 978-94-010-9598-3 (eBook)
DOI 10.1007/978-94-010-9598-3
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Contents
Forewords IX
Eiji Osawa
Part I. Plenary Lectures
Past, Present and Future of Fullerene Nanotubes: Buckytubes 3
Daniel T. Colbert and Richard E. Smalley
Novel Nanostructures: from Metal-Filled Carbon Nanotubes to
MgO Nanoferns 11
N. Grobert, W. K. Hsu, Harold W. Kroto, M. Mayne, M. Terrones,
P. Watts, R. Whitby, D. R. M. Walton and Y. Q. Zhu
Part II. Overview
Some Aspects of Fullerene Application 23
Alexander fa. Vul'
Commercial Production of Fullerenes and Carbon Nanotubes 35
Raouf o. Loutfy, Timothy P. Lowe, Alexander P. Moravsky and S. Katagiri
Part III. Nanotubular Structures
Field Emission Microscopy of Carbon Nanotubes 49
fahachi Saito, Koichi Hata, Akihiro Takahara, Kohei Matsuda,
Takayuki Kona and Chuhei Ohshima
Carbon Nanotube Field Emission Display 57
Sashiro Uemura
Thin Film Carbon Nanotube Cathodes for Field Emission
Flat Panel Display and Light Source Application 67
Alexander N. Obraztsov
Pyrolytic Carbon Nanofibers and Nanotubes:
Structure and Applications 83
Masanobu Endo, Y. A. Kim and T. Hayashi
v
Contents
From Conducting Polymers to Carbon Nanotubes:
New Horizons in Plastic Microelectronics and Carbon
Nanoelectronics 93
Liming Dai
Self-assembly of Inorganic Nanotubes Synthesized by the
Chemical Transport Reaction 113
Maja Remskar; Ales Mrzel and Francis Levy
Single-Wall Carbon Nanotubes and Single-Wall Carbon Nanohorns 125
Masako Yudasaka
FT-ICR Reaction Experiments and Molecular Dynamics
Simulations of Precursor Clusters for SWNTs 131
Shigeo Maruyama
Part IV. Medical Applications
Application and Commercial Prospects of Fullerenes in
Medicine and Biology 145
Uri Sagman
Nanomedicine: Fullerene and Carbon Nanotube Biology 155
Stephen R. Wilson
Free Radical Scavenging and Photodynamic Functions of
Micelle-like Hydrophilic Hexa(sulfobutyl)fullerene (FC S) 165
4
Yu Chi, Taizoon Canteenwala, Hans H.C. Chen, U-Ser Jeng,
Tsang-Lang Lin and Long Y. Chiang
Sonodynamic Effect of Polyethylene glycol-conjugated
Fullerene on Thmor 185
Yasuhiko Tabata, Toshihiro Ishii, Teruyoshi Aoyama,
Ryuma Oki, Yoshiaki Hirano, Osamu Ogawa and Yoshito Ikada
Part V. Hard Carbons from C
60
Mechanical Properties of Polymerized, Amorphous, and
Nanocrystalline Carbon Phases Prepared from Fullerite C
60
under Pressure 199
A.G. Lyapin
Ultrananocrystalline Diamond Films from Fullerene Precursors 217
Dieter M. Gruen
vi
Contents
Properties and Applications of Superhard and U1trahard Fullerites 223
V. Blank, S. Buga, G. Dubitsky, N. Serebryanaya,
M. Popov and V. Prokhorov
Part VI. New Source and Preparation of Fullerenes
Role of Fullerene-Iike Structures in the Reactivity of Shungite
Carbon as Used in New Materials with Advanced Properties 237
Natalia N. Rozhkova
Formation of Nanostructured Carbons under
Hydrothermal Conditions 253
Yury Gogotsi, Joseph A. Libera and Masahiro Yoshimura
Part VII. Developmental Reports
Advanced Thermal Protection Coating Using Fullerenes 267
Raouf o. Loutfy and Eugene M. Wexler
Ablative and Flame-Retardant Properties of Fullerenes 275
Raouf O. Loutfy and Eugene M. Wexler
Gas-Phase Hydrogenation of Fullemes 281
Raouf o. Loutfy and Eugene M. Wexler
Hydrogenation of Alkali Metal-Doped Fullerenes 289
Raouf o. Loutfy and Eugene M. Wexler
Unique Fullerene-Based Highly Microporous Carbons
for Gas Storage 293
Raouf o. Loutfy, Eugene M. Wexler and Weijiong Li
Use of Fullerenes and Carbon Nanotubes for Fabrication
of Efficient Electron Field Emitters 305
Raouf o. Loutfy, 1. C. Withers and Stevan T. Dimitrijevic
Aligned Carbon-Nanotubes for Sensor Applications 311
Raouf o. Loutfy and M. Hecht
Carbon Nanotube-Polycarbonate Composites 317
Raouf O. Loutfy, 1. C. Withers, M. Abdelkader and M. Sennett
vii
Contents
Physical Hydrogen Storage on Nanotubes and Nanocarbon Materials 327
Raouf O. Loutfy, A. Moravsky, A. Franco and E. Veksler
Nanotubes as Anode Material for Lithium-ion Batteries 341
Raouf 0. Loutfy, S. Hossian, A. Moravsky and M. Saleh
Fullerene Materials for Lithium-ion Battery Applications 357
Raouf 0. Loutfy and S. Katagiri
Index 369
Vlll
Forewords
We need a breakthrough
Soon after buckminsterfullerene C was finally isolated in a pure state and the antici
60
pated polyhedral structure experimentally confirmed, a variety of polymorphs of
fullerenic carbon were discovered one after the other. The shapes of these nano-sized
new carbons included perfect spheres, ellipsoids, tubes, fibers, polyhedra and further
variations, all of them still conforming to the same structural principle as C60• Scientists
were fascinated by the sudden appearance of entirely new forms of carbon that seemed
ideal construction materials for nanotechnology. In view of the small environmental
impact of carbon materials and the almost unlimited resources, many of us even felt that
we would soon be seeing the birth of carbon nanotechnology.
That was about a decade ago. As it turned out, the arrival of a new fullerene industry
was disappointingly slow. Most of the scientists working on fullerenes and carbon nano
tubes have been busy exploring and learning new properties and behaviors. The basic
research on fullerene carbons has been remarkably successful, producing well over
20000 papers within ten years. In other words, we have been producing research papers
rather than the application products. Now, many would say that 'we have done enough
lab work, let us now consider applications.' Precisely for this reason, we collect here
more than 30 reports by the world experts on the developmental research on fullerenes
and nanotubes. All the chapters are, in principle, based on invited talks presented before
a two-day International Fullerenes Workshop held in Tokyo in February 2001, but some
were thoroughly expanded after the Workshop.
The timing of our planning coincided with the decisions by the US and Japanese gov
ernments to take up 'nanotechnology' as one of the three basis technologies to be devel
oped in the 21st century. Since fullerene carbons are considered to playa central role in
nanotechnology, we hope this book will provide a handy information source to compre
hend the state of the art.
Coverage of topics in this book is by no means comprehensive due to the limitation of
pages, hence rather we emphasize a few promising areas. It is hoped that the limited
coverage is compensated at least partly by four short but excellent overview chapters by
Colbert/Smalley, Loutfy and Vul'.
Nanotubular structures are currently considered to be close to commercialization.
Uemura and Obraztsov disclose the latest advances in the hottest topic; the application
of multi-walled carbon nanotubes to flat-panel displays. Y. Saito, a pioneer in the field
emission behavior of carbon nanotubes, presents here a basic aspect of FE as a micro
scope. Dai gives a clear account of his unique developmental research in the composites
of carbon nanotubes with conducting polymers, which should find a wide market in the
near future. Endo provides a valuable account of his success story of nanofibers, which
are slightly different from nanotubes, but have many advantages for commercial appli
cations. GogotsilLiberaIYoshimura mention novel formation of nano-tubular carbons in
ix
Forewords
supercritical water. Their findings will not only stimulate discussion on the natural
occurrence of fullerenes but will also develop into industrial applications.
In view of the high cost of production of fullerenes, medical applications are defi
nitely a wise choice at this moment. Sagman is currently leading a strong drive towards
the marketing of fullerene-derived drugs, and presents a formal account on their activi
ties here for the first time. Two of the active members of his group, Wilson and Chiang,
discuss their own studies. TabatalIkada present the progress in their long and systematic
work on the photodynamic therapy of cancer by using water-soluble derivatives of C
60
as the photo-sensitizer.
The third area that we think is highly promising and will have a tremendous impact
upon wide areas of industry is the ultra-hard carbon from C polymers. Lyapin reports
60
on their systematic work on a high-pressure, high-temperature polymerization technique
performed in Russia. Working under HPHT conditions Blank and his coworkers stunned
the world by the discovery of C polymers that are harder than diamond. Here they dis
60
cuss the atomistic structure of their famous products. Gruen gives a brief account of
their unique CVD method of producing thin films of ultra-fine diamond nanoparticles
with 2-3nm diameter.
Three other chapters specifically illustrate directions of potential application in the
near future. A carbonaceous mineral of pre-Cambrian origin, Shungite, is being recog
nized as a kind of fullerene carbon. Rozhkova dicusses the possibilities of utilizing this
abundantly available carbon source for industry. Reports of Kroto's group and Remskar
represent approaches to inorganic nanotubes that are being carried out intensively in
several laboratories in the world.
We have one critical obstacle that has been hindering immediate applications of
fullerenes, and that is the still prohibitively high cost of producing fullerenes. There are
basically two approaches to this problem: either to elucidate the mechanism of forma
tion at the molecular level so that a new and more rational production method can be
designed, or to search for a breakthrough based on intelligent guess-work. The former
approach is traditionally favored in science, as exemplified by the chapters of Yudasaka
and Maruyama. The latter approach is currently being ventured by many groups around
the world but so far these have not been successful. Either way, we badly need a
breakthrough.
Finally we are blessed to have highly valuable developmental reports from Loutfy
and his group members, which consist of eleven chapters of in-depth applied research
on fullerenes and nanotubes. All the chapters in this section have not been published
before. I am particularly grateful to Dr Loutfy for his decision to choose this book for
the publishing medium of his original papers.
Last but not least I wish to express my gratitude to Mitsubishi Corporation for giving
me the rare opportunity to organize a grand Workshop fully devoted to the application
of fullerenes and to edit this book, and to all the authors who contributed chapters.
Special thanks go to the two Nobel Prize-winning pioneers, Professors Smalley and
Kroto, for joining the Workshop and contributing precious chapters.
Eiji Osawa
~obara,August2001
x
Part I
Plenary Lectures
