Gogotsi Y. (Ed.) Nanotubes and Nanofibers

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Nanotubes and Nanofibers

Advanced Materials Series

Series Editor:

Yury Gogotsi, Drexel University, Philadelphia, Pennsylvania, USA

series includes:

Carbon Nanomaterials

Yury Gogotsi

Nanotubes and Nanoﬁbers

Yury Gogotsi

Edited By

Yury Gogotsi

Drexel University,

Philadelphia, Pennsylvania, USA

CRC is an imprint of the Taylor & Francis Group,

an informa business

Boca Raton London New York

Nanotubes

and

Nanofibers

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International Standard Book Number-10: 0-8493-9387-6 (Hardcover)

International Standard Book Number-13: 978-0-8493-9387-7 (Hardcover)

Library of Congress Card Number 2006012338

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Library of Congress Cataloging-in-Publication Data

Nanotubes and nanofibers / Yury Gogotsi, editor.

p. cm.

Includes bibliographical references and index.

ISBN 0-8493-9387-6 (978-0-8493-9387-7)

1. Nanotubes. 2. Nanostructured materials. I. Gogotsi, IU. G., 1961-

TA418.9.N35N3577 2006

620’.5--dc22 2006012338

Visit the Taylor & Francis Web site at

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and the CRC Press Web site at

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This book is dedicated to my father, Professor George Gogotsi,

who inspired me to become a scientist.

Preface

Nanomaterials, which are materials with structural units on a nanometer scale in at least one direction,

is the fastest growing area in materials science and engineering. Material properties become different

on the nanoscale: for example, the theoretical strength of materials can be reached or quantum effects

may appear. One-dimensional and quasi-one-dimensional materials such as nanotubes and nanowires

demonstrate many extreme properties that can be tuned by controlling their structure and diameter.

Nanotubes, nanowires, and nanofibers are not only excellent tools for studying one-dimensional

phenomena, but they are also certainly among the most important and promising nanomaterials and

nanostructures. The role of nanomaterials in industries is growing. Nanofibers are already used for

insulation and reinforcement of composites, and many materials and structures incorporating

nanotubes and nanowires are under development. Extensions to other tubular and rodlike or wirelike

structures provide the scope for new discoveries and novel applications.

This book describes a large variety of nanotubes, nanofibers, and related structures such as

whiskers and nanowires. This area is very broad; it is impossible to cover all fibrous nanomaterials

in a single volume. Carbon nanotubes (

Chapters 1 and 2) receive special attention in this book

because carbon is as important for nanotechnology as silicon is for electronics. Sumio Iijima's dis-

covery of carbon nanotubes in 1991 stimulated the development of the whole nanotechnology field.

Since then, a dramatic progress in synthesis and purification of nanotubes has been achieved and

many applications have emerged. After carbon, many other materials have been produced in the

tubular shape with nanometer diameters.

Designed specifically to provide an overview of nanotubes and nanofibers for today's scientists,

graduate students, and engineering professionals, the book will offer a treatment of subjects using

terms familiar to a materials scientist or engineer. The book consists of eight chapters selected from

the recently published Nanomaterials Handbook and is written by the leading researchers in the

field. Providing coverage of the latest material developments in the United States, Asia, Europe, and

Australia, the book describes both commercially available and emerging materials.

Finally, I would like to acknowledge all the people who have been helpful in making this book

possible. My family was very patient and understanding, and my students and postdocs did a great

job allowing me to concentrate on the book project. The staff of Taylor & Francis helped

immensely.

Yury Gogotsi

Philadelphia, PA

Editor

Dr. Yury Gogotsi is professor of materials science and engineering at Drexel University in

Philadelphia, Pennsylvania. He also holds appointments in the Departments of Chemistry and

Mechanical Engineering at Drexel University and serves as director of the A.J. Drexel

Nanotechnology Institute and associate dean of the College of Engineering. He received his M.S.

(1984) and Ph.D. (1986) degrees from Kiev Polytechnic and a D.Sc. degree from the Institute of

Materials Science, Ukrainian Academy of Science, in 1995. His research group works on carbon

nanotubes, nanoporous carbide-derived carbons, and nanofluidics. He has also contributed to the

areas of structural ceramics, corrosion of ceramic materials, and pressure-induced phase transfor-

mations, creating a new research field called high pressure surface science and engineering. He has

coauthored 2 books, edited 9 books, obtained more than 20 patents, and authored about 200 jour-

nal papers and 12 book chapters. He has advised a large number of M.S., Ph.D., and post-doctoral

students at Drexel University and University of Illinois at Chicago.

Gogotsi has received several awards for his research, including I.N. Frantsevich Prize from the

Ukrainian Academy of Science, S. Somiya Award from the International Union of Materials

Research Societies, G.C. Kuczynski Prize from the International Institute for the Science of

Sintering, and Roland B. Snow Award from the American Ceramic Society (twice). He has been

elected a fellow of the American Ceramic Society, academician of the World Academy of Ceramics,

and full member of the International Institute for the Science of Sintering.

Ying Chen

Department of Electronic Materials

Engineering

Research School of Physical Sciences and

Engineering

The Australian National University

Canberra, Australia

Svetlana Dimovski

Department of Materials Science and

Engineering

Drexel University

Philadelphia, Pennsylvania

Fangming Du

Department of Chemical and Biomolecular

Engineering

University of Pennsylvania

Philadelphia, Pennsylvania

John E. Fischer

Department of Materials Science and

Engineering

University of Pennsylvania

Philadelphia, Pennsylvania

Yury Gogotsi

Department of Materials Science and

Engineering

Drexel University

Philadelphia, Pennsylvania

Frank K. Ko

Department of Materials Science and

Engineering

Drexel University

Philadelphia, Pennsylvania

Eduard G. Rakov

D.I. Mendeleev University of Chemical

Technology

Moscow, Russia

Jonathan E. Spanier

Department of Materials Science and

Engineering

Drexel University

Philadelphia, Pennsylvania

R. Tenne

Department of Materials and Interfaces

Weizmann Institute

Rehovot, Israel

Karen I. Winey

Department of Materials Science and

Engineering

University of Pennsylvania

Philadelphia, Pennsylvania

Hongzhou Zhang

Department of Electronic Materials

Engineering

Research School of Physical Sciences and

Engineering

The Australian National University

Canberra, Australia

Contributors

Table of Contents

Chapter 1 Carbon Nanotubes: Structure and Properties................................................................1

John E. Fischer

Chapter 2 Chemistry of Carbon Nanotubes ................................................................................37

Eduard G. Rakov

Chapter 3 Graphite Whiskers, Cones, and Polyhedral Crystals ................................................109

Svetlana Dimovski and Yury Gogotsi

Chapter 4 Inorganic Nanotubes and Fullerene-Like Materials of Metal Dichalcogenide

and Related Layered Compounds.............................................................................135

R. Tenne

Chapter 5 Boron Nitride Nanotubes: Synthesis and Structure..................................................157

Hongzhou Zhang and Ying Chen

Chapter 6 Nanotubes in Multifunctional Polymer Nanocomposites.........................................179

Fangming Du and Karen I. Winey

Chapter 7 One-Dimensional Semiconductor and Oxide Nanostructures..................................199

Jonathan E. Spanier

Chapter 8 Nanofiber Technology...............................................................................................233

Frank K. Ko

Carbon Nanotubes: Structure

and Properties

John E. Fischer

Department of Materials Science and Engineering,

University of Pennsylvania, Philadelphia, Pennsylvania

CONTENTS

1.1 Introduction .............................................................................................................................1

1.2 Structure ..................................................................................................................................3

1.2.1 Single-Wall Tubes, Bundles, and Crystalline Ropes ...................................................3

1.2.2 Multiwall Tubes ...........................................................................................................5

1.2.3 Macroscopic Nanotube Materials ................................................................................5

1.2.4 Fibers ...........................................................................................................................7

1.2.5 Filled Tubes ..................................................................................................................7

1.2.6 Nanotube Suspensions ...............................................................................................10

1.3 Physical Properties ................................................................................................................11

1.3.1 Mechanical Properties ...............................................................................................12

1.3.2 Thermal Properties ....................................................................................................13

1.3.3 Electronic Properties .................................................................................................18

1.3.4 Magnetic and Superconducting Properties ................................................................30

1.4 Summary and Prospects ........................................................................................................31

Acknowledgments ...........................................................................................................................31

References ......................................................................................................................................31

1.1 INTRODUCTION

Carbon nanotubes were discovered in 1991 as a minor by-product of fullerene synthesis [1].

Remarkable progress has been made in the ensuing 14 years, including the discovery of two basic

types of nanotubes (single-wall and multiwall); great strides have been taken in their synthesis and

purification, elucidation of the fundamental physical properties, and important steps are being taken

toward realistic practical applications.

Carbon nanotubes are long cylinders of 3-coordinated carbon, slightly pyramidalized by curvature

[2] from the pure sp

hybridization of graphene, toward the diamond-like sp

. Infinitely long in prin-

ciple, a perfect tube is capped at both ends by hemi-fullerenes, leaving no dangling bonds. A single-

walled carbon nanotube (SWNT) is one such cylinder, while multiwall tubes (MWNT) consist of

many nested cylinders whose successive radii differ by roughly the interlayer spacing of graphite (see

Figure 6.1 in the chapter by Du and Winey [3]). The minimum diameter of a stable freestanding

SWNT is limited by curvature-induced strain to ~0.4 nm [4]. MWNT may have outer shells ⬎30 nm