2308_half 11/22/05 10:46 AM Page 1 NANOMATERIALS HANDBOOK Copyright 2006 by Taylor & Francis Group, LLC 2308_title 11/22/05 10:46 AM Page 1 NANOMATERIALS HANDBOOK EDITED BY YURY GOGOTSI A CRC title, part of the Taylor & Francis imprint, a member of the Taylor & Francis Group, the academic division of T&F Informa plc. Boca Raton London New York Copyright 2006 by Taylor & Francis Group, LLC The upper left image on the cover is a colored SEM micrograph of a nano-lamina of graphite produced by chlorination of iron carbide. The upper right image is a colored SEM micrograph of a graphite polyhedral crystal (GPC) with its Raman spectra in the foreground. Both images are by S. Dimovski, Drexel University. The lower image is a molecular dynamics simulation of zipping of a graphene edge (by S.V.Rotkin, Lehigh). Similarities between a sleeve formed at the edge of graphite and a single-wall nanotube can be clearly seen. The background (by J. Libera) is a TEM image of the GPC edge. Artist view by B. Grosser, ITG, Beckman Institute, UIUC). See chapters 6 and 8 for more information. Published in 2006 by CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2006 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group No claim to original U.S. Government works Printed in the United States of America on acid-free paper 10987654321 International Standard Book Number-10: 0-8493-2308-8 (Hardcover) International Standard Book Number-13: 978-0-8493-2308-9 (Hardcover) Library of Congress Card Number 2005053105 This book contains information obtained from authentic and highly regarded sources. Reprinted material is quoted with permission, and sources are indicated. A wide variety of references are listed. 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Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Library of Congress Cataloging-in-Publication Data Nanomaterials handbook / [edited by] Yuri Gogotsi. p. cm. Includes bibliographical references and index. ISBN 0-8493-2308-8 1. Nanostructured materials Handbooks, manuals, etc. I. Gogotsi, IU. G., 1961- TA418.9.N35H357 2006 620.1'1 dc22 2005053105 Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com Taylor & Francis Group is the Academic Division of Informa plc. 2308_Discl.fm Page 1 Thursday, December 22, 2005 11:28 AM Copyright 2006 by Taylor & Francis Group, LLC This book is dedicated to my family — the source of my inspiration CRC_2308_Prelims.qxd 12/3/2005 12:09 PM Page v Copyright 2006 by Taylor & Francis Group, LLC Preface Nanomaterials Handbook is designed specifically to provide an overview of nanomaterials for today’s scientists, graduate students, and engineering professionals. The study of nanomaterials, which are materials with structural units (grains or particles) on a nanometer scale in at least one direction, is the fastest growing area in material science and engineering. Material properties change on the nanoscale; for example, the theoretical strength of materials can be reached or quantum effects may appear. Thus, nanomaterials may have properties different from those of single crystals or conventional microstructured, monolithic, or composite materials. Man has been taking advantage of nanomaterials for a long time. Roman glass artifacts (e.g., the famous Lycurgus cup located in the British Museum in London) contained metal nanoparticles, which provided beautiful colors. In medieval times, metal nanoparticles were used to color glass for cathedral windows. For example, the famous gold ruby glass contains nanometer-size gold particles that impart the glass its red color. Currently, nanomaterials play a role in numerous industries, e.g., (1) carbon black particles (about 30nm in size) make rubber tires wear-resistant; (2) nano phos- phors are used in LCDs and CRTs to display colors; (3) nanofibers are used for insulation and rein- forcement of composites; (4) nano-size alumina and silica powders are used for fine polishing of silicon wafers; (5) nanoparticles of iron oxide create the magnetic material used in disk drives and audio/video tapes; (6) nano-zinc oxide or titania is used in sunscreens to block UV rays from the sun; and (7) nanoscale-platinum particles are crucial to the operation of catalytic converters. Many new nanomaterials, such as nanotubes, fullerenes, and quantum dots, have emerged recently and many others are under development. The handbook uses terms familiar to a materials scientist or engineer and describes nanomate- rials, but not nanotechnology in general. The nanomaterials area alone is so broad that it is virtually impossible to cover all materials in a single volume. Carbon-based materials receive special atten- tion in this book, because carbon is as important to nanotechnology as silicon is to electronics. The materials will not only be divided into traditional classes such as ceramics, semiconductors, metals, biomaterials, and polymers; but also will be treated based on their dimensionality, processing meth- ods, and applications. A variety of applications, ranging from drug delivery systems and field-emis- sion displays to machine tools and bioimplants will be described. Both commercially available and emerging materials will be covered. The handbook consists of 27 chapters written by leading researchers from academia, national laboratories, and industry, and covers the latest material devel- opments in America, Asia, Europe, and Australia. Finally, I would like to acknowledge all people who have been helpful in making this book pos- sible. My family has been very patient and understanding. My students and postdocs helped me concentrate on the book project and Taylor & Francis staff helped me immensely. CRC_2308_Preface.qxd 12/21/2005 5:49 PM Page ix Copyright 2006 by Taylor & Francis Group, LLC Editor Yury Gogotsi is professor of materials science and engineering at Drexel University, 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 Ukrainian Academy of Science in 1995. His research group works on carbon nanotubes, nanoporous carbide-derived carbons, and nanoflu- idics. He has also contributed to the areas of structural ceramics, corrosion of ceramic materials, and pressure-induced phase transformations. He has coauthored 2 books, edited 7 books, obtained 20 patents, and authored more than 200 research papers. He has advised a number of M.S., Ph.D., and postdoctoral students at Drexel University and University of Illinois at Chicago. Gogotsi 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, Kuczynski Prize from the International Institute for the Science of Sintering, and Roland B. Snow Award from the American Ceramic Society. 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. CRC_2308_AbEditor.qxd 11/25/2005 3:45 PM Page xi Copyright 2006 by Taylor & Francis Group, LLC Rostislav A. Andrievski Institute of Problems of Chemical Physics Russian Academy of Sciences Chernogolovka, Russia Michel W. Barsoum Department of Materials Science and Engineering Drexel University Philadelphia, Pennsylvania François Béguin Centre de Recherche sur la Matière Divisée CNRS-Université Orléans, France J.D. Carey Advanced Technology Institute University of Surrey Guildford, United Kingdom A.K. Cheetham University of California Santa Barbara, California I-Wei Chen University of Pennsylvania Philadelphia, Pennsylvania Mingwei Chen Tohoku University Sendai, Japan Ying Chen Department of Electronic Materials Engineering Research School of Physical Science and Engineering The Australian National University Canberra, Australia D. Davis Louisiana State University Baton Rouge, Louisiana Svetlana Dimovski Department of Materials Science and Engineering Drexel University Philadelphia, Pennsylvania Mildred S. Dresselhaus Massachusetts Institute of Technology Cambridge, Massachusetts Fangming Du Department of Chemical and Biomolecular Engineering University of Pennsylvania Philadelphia, Pennsylvania Ali Erdemir Argonne National Laboratory Argonne, Illinois Osman Levent Eryilmaz Argonne National Laboratory Argonne, Illinois John E. Fischer Department of Materials Science and Engineering University of Pennsylvania Philadelphia, Pennsylvania Elzbieta Frackowiak Institute of Chemistry and Technical Electrochemistry Poznan´ University of Technology Poznan´ , Poland Yury Gogotsi Department of Materials Science and Engineering Drexel University Philadelphia, Pennsylvania Contributors CRC_2308_Loc.qxd 12/1/2005 3:26 PM Page xiii Copyright 2006 by Taylor & Francis Group, LLC Z. Guo Louisiana State University Baton Rouge, Louisiana Meredith L. Hans Department of Materials Science and Engineering Drexel University Philadelphia, Pennsylvania Kevin Hemker Johns Hopkins University Baltimore, Maryland Joseph P. Heremans The Ohio State University Columbus, Ohio Q. Huang Louisiana State University Baton Rouge, Louisiana Pavel E. Kazin Moscow State University Moscow, Russia Kursat Kazmanli Istanbul Technical University Istanbul, Turkey Frank K. Ko Department of Materials Science and Engineering Drexel University Philadelphia, Pennsylvania Y. Li Louisiana State University Baton Rouge, Louisiana Anthony M. Lowman Department of Materials Science and Engineering Drexel University Philadelphia, Pennsylvania A. Lozano-Morales Louisiana State University Baton Rouge, Louisiana En Ma Johns Hopkins University Baltimore, Maryland R.A. Masumura Naval Research Laboratory Washington, D.C. Aurelio Mateo-Alonso Dipartimento di Scienze Farmaceutiche Università degli Studi di Trieste Piazzale Europa, Italy Gary McGuire International Technology Center Research Triangle Park, North Carolina Nikhil Mehta Auburn University Auburn, Alabama A. Nikitin Department of Materials Science and Engineering Drexel University Philadelphia, Pennsylvania I.A. Ovid’ko Institute of Problems of Mechanical Engineering Russian Academy of Sciences Moscow, Russia Giuseppe R. Palmese Department of Materials Science and Engineering Drexel University Philadelphia, Pennsylvania A. Panda Louisiana State University Baton Rouge, Louisiana C.S. Pande Naval Research Laboratory Washington, D.C. Nicholas A. Peppas University of Texas Austin, Texas E.J. Podlaha Louisiana State University Baton Rouge, Louisiana CRC_2308_Loc.qxd 12/1/2005 3:26 PM Page xiv Copyright 2006 by Taylor & Francis Group, LLC Maurizio Prato Dipartimento di Scienze Farmaceutiche Università degli Studi di Trieste Piazzale Europa, Italy Barton Prorok Auburn University Auburn, Alabama Eduard G. Rakov D.I. Mendeleev University of Chemical Technology Moscow, Russia Vijay I. Raman Department of Materials Science and Engineering, Drexel University Philadelphia, Pennsylvania C.N.R. Rao Jawaharlal Nehru Centre for Advanced Scientific Research Bangalore, India Michiko Sato Purdue University West Lafayette, Indiana Olga Shenderova International Technology Center Research Triangle Park, North Carolina S.R.P. Silva Advanced Technology Institute University of Surrey Guildford, United Kingdom Amit Singhal NEI Corporation Piscataway, New Jersey Ganesh Skandan NEI Corporation Piscataway, New Jersey Jonathan E. Spanier Department of Materials Science and Engineering Drexel University Philadelphia, Pennsylvania Nikos Tagmatarchis Dipartimento di Scienze Farmaceutiche Università degli Studi di Trieste Piazzale Europa, Italy R. Tenne Department of Materials and Interfaces Weizmann Institute Rehovot, Israel J. Brock Thomas University of Texas Austin, Texas Yuri D. Tretyakov Moscow State University Moscow, Russia Mustafa Urgen Istanbul Technical University Istanbul, Turkey Xiao-Hui Wang Tsinghua University Beijing, China Thomas J. Webster Purdue University West Lafayette, Indiana Karen I. Winey Department of Materials Science and Engineering University of Pennsylvania Philadelphia, Pennsylvania G. Yushin Department of Materials Science and Engineering Drexel University Philadelphia, Pennsylvania Hongzhou Zhang Department of Electronic Materials Engineering Research School of Physical Sciences and Engineering The Australian National University Canberra, Australia J. Zhang Louisiana State University Baton Rouge, Louisiana CRC_2308_Loc.qxd 12/1/2005 3:26 PM Page xv Copyright 2006 by Taylor & Francis Group, LLC Table of Contents Chapter 1 Materials Science at the Nanoscale C.N.R. Rao and A.K. Cheetham Chapter 2 Perspectives on the Science and Technology of Nanoparticle Synthesis Ganesh Skandan and Amit Singhal Chapter 3 Fullerenes and Their Derivatives Aurelio Mateo-Alonso, Nikos Tagmatarchis, and Maurizio Prato Chapter 4 Carbon Nanotubes: Structure and Properties John E. Fischer Chapter 5 Chemistry of Carbon Nanotubes Eduard G. Rakov Chapter 6 Graphite Whiskers, Cones, and Polyhedral Crystals Svetlana Dimovski and Yury Gogotsi Chapter 7 Nanocrystalline Diamond Olga Shenderova and Gary McGuire Chapter 8 Carbide-Derived Carbon G. Yushin, A. Nikitin, and Y. Gogotsi Chapter 9 One-Dimensional Semiconductor and Oxide Nanostructures Jonathan E. Spanier Chapter 10 Inorganic Nanotubes and Fullerene-Like Materials of Metal Dichalcogenide and Related Layered Compounds R. Tenne Chapter 11 Boron Nitride Nanotubes: Synthesis and Structure Hongzhou Zhang and Ying Chen CRC_2308_contents.qxd 12/5/2005 9:33 AM Page xvii Copyright 2006 by Taylor & Francis Group, LLC [...]... success in the synthesis of nanomaterials in conjunction with the advent of tools for characterization and manipulation The synthesis of nanomaterials spans inorganic, organic, and biological systems on manipulation (Table 1.2) The subsequent assembling of the individual nanostructures into Copyright 2006 by Taylor & Francis Group, LLC CRC_2308_Ch001.qxd 1/3/2006 2:54 PM Page 6 6 Nanomaterials Handbook... for structure, dynamics, response, and transport in nanostructures Applications of nanomaterials in biology, medicine, electronics, chemical processes, high-strength materials, etc Nanoscience and nanotechnology have grown explosively in the last decade, because of the increasing availability of methods of synthesis of nanomaterials as well as tools of characterization and manipulation (Table 1.2) Several... the nanoscale is, however, of recent origin The present goals of the science and technology of nanomaterials are to master the synthesis of nanostructures (nano-building units) and their assemblies of desired properties; to explore and establish nanodevice concepts; to generate new classes of high-performance nanomaterials, including biology-inspired systems; and to improve techniques for the investigation... and nanotubes, while collections of nanostructures involve arrays, assemblies, and superlattices of the individual nanostructures [1,2] Table 1.1 lists typical dimensions of nanomaterials The physical and chemical properties of nanomaterials can differ significantly from those of the atomic-molecular or the bulk materials of the same composition The uniqueness of the structural characteristics, energetics,... dots and nanotubes have been modeled satisfactorily First principles calculations of nanomaterials can be problematic if the clusters are too large to be treated by Hartree–Fock methods and too small for density functional theory Copyright 2006 by Taylor & Francis Group, LLC CRC_2308_Ch001.qxd 1/3/2006 2:54 PM Page 10 10 Nanomaterials Handbook 1.6 APPLICATIONS By employing sol–gels and aerogels, inorganic... inorganic nanodevice with such a biological motor Other areas of biology in which nanomaterials can have an impact are the monitoring of the environment and living systems by the use of nanosensors and the improvement of prosthetics used to repair or replace parts of the human body The most significant applications of nanomaterials may be in nanodevices and nanoelectronics [1,12,18] There are already... every reason to believe that there will be much progress in the coming decade REFERENCES 1 Rao, C.N.R., Muller, A., and Cheetham, A.K., Eds., Chemistry of Nanomaterials, Wiley-VCH, Weinheim, 2004 2 Rao, C.N.R and Cheetham, A.K., Science and Technology of Nanomaterials, J Mater Chem., 11, 2887, 2001 3 Feynmann, R.P., Miniaturization, Reinhold, New York, 1961 4 Lehn, J.M., Supramolecular Chemistry, VCH, Weinheim,... The field has matured so rapidly and so fast that it is probably hard to find a segment of any technical subject where the implications of nanomaterials have not been explored at least to a preliminary extent Studies are being conducted on the potential use of nanomaterials in diverse applications, including hydrogen storage [6,7], ion-sensing and gas sensing [8], surface-modified nanoparticles for... relate to size effects, shape phenomena, quantum confinement, and response to external electric and optical excitations of individual and coupled finite systems Size effects are an essential aspect of nanomaterials The effects determined by size pertain to the evolution of structural, thermodynamic, electronic, spectroscopic, and chemical features of these finite systems with increasing size Size effects... of 1 to 2 nm diameter exhibit unexpected catalytic activity, as exemplified by nanocatalysis by gold particles Copyright 2006 by Taylor & Francis Group, LLC CRC_2308_Ch001.qxd 1/3/2006 2:54 PM Page 4 4 Nanomaterials Handbook Energy Metals Isolated atom Nanocrystal Bulk Unoccupied EF Occupied Density of states Unoccupied Energy Semiconductors EF Occupied Density of states FIGURE 1.1 Density of states . I. Winey Chapter 21 Nanoporous Polymers — Design and Applications Vijay I. Raman and Giuseppe R. Palmese Chapter 22 Nanotechnology and Biomaterials J. Brock Thomas, Nicholas A. Peppas, Michiko. by Taylor & Francis Group, LLC Shapes of nanoparticles also play a role in determining properties, such as reactivity and elec- tronic spectra. For example, the position of the plasmon band. inspiration CRC_2308_Prelims.qxd 12/3/2005 12:09 PM Page v Copyright 2006 by Taylor & Francis Group, LLC Preface Nanomaterials Handbook is designed specifically to provide an overview of nanomaterials for today’s