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CARBON ALLOYS NOVEL CONCEPTS TO DEVELOP CARBON SCIENCE AND TECHNOLOGY E. YASUDA, M. INAGAKI, K. KANEKO, 0, A. OYA & Y. TAN ELSEVIER CARBON ALLOYS Novel Concepts to Develop Carbon Science and Technology Elsevier Science Internet Homepage - http:/hvww.elsevier.com Consult the Elscvier homepage for full catalogue information on all books, journals and electronic products and scrvices. Related JournalslProduets Free specimen cryygladly sent on request. Elsevier Science Ltd, The Boulevard. Langford Lane, Kidlingtun, Oxford, OX5 IGB, UK Applied Surface Science Carbon Chemical Physics Chemical Physics Lettcrs Diamond and Relatcd Materials Journal of Power Sourccs Surface and Coatings Technology Surfacc Science Thin Solid Films Elsevier Titles of Related Interest BURCHELL Carbon Materials for Advanced Technologies ISBN: 008-042683-2 DRESSELHAUS & DRESSELHAUS Science of Fullercncs and Carbon Nanotubes: Their Properties and Applications ISBN: 0122218205 INAGAKl New Carbons -Control of Structure and Functions ISBN: 008-043713-3 MARSH Activatcd Carbon Compendium ISBN: 008-044030-4 TANAKA, YAMABE & FUKUl The Scicncc and Technology of Carbon Nanotubcs ISBN: 008-042696-4 To Contact the Publisher Elscvicr Science welcomes enquiries concerning publishing proposals: books, journal special issues, conference procccdings, etc. All formats and media can bc considered. Should you hdvc a publishing proposal you wish to discuss, please contact, without obligation, the publisher responsible for Elsevicr’s materials chemistry programmc: lain Craig Publishing Editor Elsevier Science Ltd The Boulevard, Langford Lane Phone: f44 1865 843631 Kidlington, Oxford Fax: +44 1865 843920 OX5 IGB, UK E-mail: i.craig@elsevicr.com General enquiries, including placing ordcrs, should be directed to Elscvicr’s Rcgional Sales Offices ~ please access the Elsevier homcpage for full contact details (homepage details at thc top of this page). CARBON ALLOYS Novel Concepts to Develop Carbon Science and Technology Edited by Ei-ichi YASUDA Michio INAGAKI Katsumi KANEKO Morinobu END0 Asao OYA Yasuhiro TANABE 2003 AMSTERDAM -BOSTON -LONDON - NEW YORK - OXFORD -PARIS SAN DIEGO - SAN FRANCISCO - SINGAPORE - SYDNEY - TOKYO ELSEVIER SCIENCE Ltd The Boulevard, Langford Lanc Kidlington, Oxford OX5 IGB, UK 0 2003 Elsevier Science Ltd. All rights reserved. This work is protccted undcr copyright by Elsevier Science, and the following terms and conditions apply to its use: Photocopying Single photocopies of singlc chapters may bc made for personal use as allowcd by national copyright laws. Permission of the Publishcr and payment of a fee is rcquired for all other photocopying, including multiple or systematic copying, copying for advcrtising or promotional purposcs, resale, and all forms of documcnt dclivery. Special rates are available for educational institutions that wish to makc photocopies for non-profit cducational classroom use. Permissions may be sought dircctly from Elsevier Science via their homepagc (http://www.clsevier.com) by sclccting ‘Customer support’ and then ‘Permissions’. Altcrnatively you can scnd an c-mail to: permissions(~clscvier.com, or fax to: (f44) 1865 853333. In the USA, users may clear pcrmissions and makc payments through the Copyright Clearance Center, Inc., 222 Roscwood Drive, Danvcrs, MA 01923, USA; phone: (+ 1) (978) 7508400, fax: (+ 1) (978) 7504744, and in the UK through the Copyright Liccnsing Agcncy Rapid Clearance Service (CLARCS), YO Tottcnham Court Road, London WlP OLP, UK; phone: (+44) 207 631 5555; fax: (+44) 207 631 5500. Other countries may havc a local reprographic rights agency for paymcnts. DeriVdtiVC Works Tables of contcnts may be reproduccd for internal circulation, but permission of Elsevier Science is rcquired for external resale or distribution of such material. Permission of the Publisher is rcquired for all other derivative works, including compilations and translations. Electronic Storage or Usage Permission of thc Publishcr is requircd to storc or use electronically any material contained in this work, including any chapter or part of a chapter. Except as outlined above, no part of this work may bc rcproduccd, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without prior written permission of thc Publisher. Address permissions requcsts to: Elscvicr Science Global Rights Departmcnt. at the fax and e-mail addresses notcd above. Noticc No responsibility is assumed by thc Publisher for any injury and/or damage to persons or property as a matter of products liability, ncgligcnce or othcnvise, or from any use or operation of any methods, products, instructions or ideas contained in thc material hcrein. Because of rapid advances in the medical xiences, in particular, indcpcndent verification of diagnoses and drug dosages should be made. First edition 2003 Library of Congress Cataloging in Publication Data A catalog rccord from thc Library of Congress has been applied for. British Library Cataloguing in Publication Data A catalogue record from the British Library has been applied for. ISBN: 0 08 044163 7 @ The paper used in this publication meets the requirements of ANSIMISO 239.48-1992 (Permanence of Paper). Printed in The Netherlands. V Contents Preface xiii Part 1 . Introduction Chapter 1 . Introduction 3 1 AShortHistory 3 2 CarbonFamily 5 3 CarbonAlloys 9 References 11 Ei-ichi Yasuda and Michio Inagaki Part 2 . Space Control in Carbon Alloys Chapter 2 . Hybrid Orbital Control in Carbon Alloys 15 Hybridization in a Carbon Atom 15 2 Defect StatesandModificationsof theHybridization 27 Spectroscopies for sp” Structure 33 4 Conclusions 38 References 38 Atomic and Molecular Scales 41 1 . Introduction 41 2 . Intercalation Compounds 42 Insertion of Li Ions into the Disordered Carbon Materials 44 4 Substitution of Heteroatoms 46 5 Metal-doped Fullerenes 49 Metal-doped Carbon Nanotubes 50 7 Conclusions 54 Chapter 4 . Surface and Hidden Surface-controlled Carbon Alloys 57 Materials 57 Carbon Structure of Superhigh Surface Area 64 Design of Hidden Surfaces with Alloying 65 Riichiro Saito 1 3 Chapter 3 . Structural Design and Functions of Carbon Materials by Alloying in Morinobu Endo. Takuya Hayashi, YoongAhm Kim. Hiroaki Ohta and Sung Wha Hong 3 6 References 54 Katsumi Kaneko 1 2 3 Importance of Hidden Surfaces and Confined Spaces in Carbon vi Contents 4 5 Properties of Hidden Surface- or Pore Space-alloyed Carbons 68 Design of New Porous Carbon with Carbon Alloying Technique 76 References 77 Chapter 5 . Control of Interface and Microstructure in Carbon Alloys 83 1 Introduction 83 2 Interface Control 85 3 Microstructure Control 89 4 Conclusion 93 References 93 Yasuhiro Tanabe and Ei-ichi Yasuda Part 3 . Typical Carbon Alloys and Processing Chapter 6 . Intercalation Compounds 99 1 Introduction 99 Li-insertion into Carbon Materials 100 Carbon Materials 103 Alkali Metals 104 Boehmite with Layered Structure 105 6 Conclusion 105 References 106 Chapter 7 . Porous Carbon 109 1 Introduction 109 Control of Pore Structure 110 Performance of Advanced Porous Carbon 118 4 Conclusions. 123 References 124 Noboru Akzuawa 2 3 4 5 New Intercalation Compounds Prepared from Unique Host Host Effect on the lntercalation of Halogen Molecules and Physical Properties of MC1,. GICs and Alkyl Derivative of Takashi Kyotani 2 3 Chapter 8 . Polymer Blend Technique €or Designing Carbon Materials 129 Asao @a 2 . 3 5 1 . Introduction 129 Porous Carbon Materials 129 4 Carbon Nanofibers and Carbon Nanotubes 133 Other Fibrous Carbon Materials with Unique Shapes 139 6 Conclusions 141 References 141 Preferential Support of Metal Particles on Pore Surface 131 Part 4 . The Latest Characterization Techniques Chapter 9 . Computer Simulations 145 Shinji Tsuneyuki 1 Methods., 145 vii 2 Applications 150 3 Conclusions 156 References 156 Chapter 10 . X-ray Diffraction Methods to Study Crystallite Size and Lattice Constants of Carbon Materials 161 1 . Introduction 161 Measurement Method (JSPS Method) 162 Temperatures 170 References 173 Scattering 175 1 . Introduction 175 Fundamentals of Small-Angle X-ray Scattering 176 3 Analyses 180 Examples of Structure Determination 183 References 187 Minoru Shiraishi and Michio Znagaki 2 3 Characterization of Carbonized Materials Heat-treated at Low Chapter 11 . Pore Structure Analyses of Carbons by Small-Angle X-ray Keiko Nishikawa 2 . 4 Chapter 12 . XAFS Analysis and Applications to Carbons and Catalysts 189 Hiromi Yamashita 1 Introduction 189 2 XAFSAnalysis 190 Applications to Carbon Related Materials and Catalysts 200 XAFS in the Future 207 References 207 3 4 Chapter 13 . X-Ray Photoelectron Spectroscopy and its Application to Carbon . 211 Noboru Suzuki 2 3 1 Introduction and XPS 211 Cls Binding Energy 212 Application to Carbon Materials 212 References 220 Chapter 14 . Transmission Electron Microscopy 223 1 Introduction 223 Materials Characterization by Means of TEM 223 Specimen Preparation by FIB 231 In-Situ Heating Experiment 235 References 238 Characterization of Carbon Materials 239 1 Introduction 239 Basic Principles of EELS and Instrumentation 240 Hiroyasu Saka 2 3 4 Chapter 15 . Electron Energy-Loss Spectroscopy and its Applications to Hisako Hirai 2 [...]... strategy for the development of carbon materials, called carbon alloys, has been implemented in Japan which has resulted in success for developments in carbon science and technology Keyword: Carbon materials, Classic carbons, New carbons, Carbon family, Carbon alloys 1 A Short History Carbon materials have attracted the attention of human beings from prehistoric times Carbon materials include charcoals... compounds 1980 i -carbon films Isotropic high-densitygraphites Carbon fiber-reinforcedconcrete 1985 Buckminsterfullerene C , 1990 Superconductivityof KC, ,,; Carbon nanotube single-wall and multiwall; Proposal of the concept of carbon alloys 1995 Storage of hydrogen in carbon nanofilaments Carbon prostheses Mesocarbon microbeads Carbon electrode for fuel cell First wall for fusion reactor Carbon anode... create quite different carbon components We hope that this bookwill be a major reference source for those working with carbon alloys The book is divided into five parts: (1) definitions and approaches to carbon alloys; (2) analyses of results in terms of controlling the locations of other alloying elements; (3) typical carbon alloys and their preparation; (4) characterization of carbon alloys; and (5) development... in carbon materials, with such a wide range of structures, textures and properties, and also because of the great demands on materials science from modern technology, a new concept or strategy for the development of carbon materials was needed The Japanese Carbon Group proposed a new strategy, Le., carbon alloys in 1992 [6] The following definition of carbon alloys was tentatively suggested: Carbon alloys. .. proposed for amorphous carbon films in Fig 4 [7] shows that such alloying gives variety in carbon materials Amorphous carbons, which so far have been classified into one category, can be considered as carbon alloys using sp3 and sp2 hybrid orbitals, in addition to bonding with hydrogen In this definition of carbon alloys, porous carbons can be understood as a combination of carbon atoms and nanospaces... alloys, substitutional alloys, intercalation alloys, surfaceand/or hidden surface controlled alloys, and microstructure controlled alloys Special attention was paid to space control and function development by alloying with carbons The formation of carbon alloys may be considered as the filling of space by carbon atoms with different hybrid orbitals and foreign atoms, because sp3 carbon gives three-dimensional... carbon blacks and activated carbons) have a long history of usage and are called classic carbon materials, in contrast to newly developed carbon materials the so-called new carbons Carbon materials play a part in our daily lives in various ways, many not being that obvious For example, among the new carbons there are carbon fibers for reinforcing rackets and fishing rods, activated carbons as filters for... 122-127,1997 Y Tanabe and E Yasuda, Carbon alloys Carbon, 38: 329-334,1995 P.K Bachmann, Ullman’s Encyclopedia of Industrial Chemistry, Vol A26, pp 72-25, 1996 M Inagaki (Ed.) Creation of functional nano- and micro-sized spaces in carbon materials Special issue of Synthetic Metals, 125: 139-266,2002 Part 2 Space Control in Carbon Alloys 15 Chapter 2 Hybrid Orbital Control in Carbon Alloys Riichiro Saito* Department... composed of carbon atoms in multi-component systems, in which each component has physical andlor chemical interactions with each other Here, carbons with different hybrid orbitals account as difierent components Chapter I 10 Polyethyne iC.HJ- Fig 4 Classification diagram for amorphous carbon films [ ] 7 According to this definition, most carbon materials are carbon alloys (homoatomic alloys) , as mentioned... structure and property The concept of Carbon Alloys was initiated in Japan as a national project and is now recognized internationally Carbon Alloys are defined as being materials mainly composed of carbon materials in multi-component systems, the carbon atoms of each component having physical andlor chemical interactive relationships with other atoms or compounds The carbon atoms of the components may . and technology. Keyword: Carbon materials, Classic carbons, New carbons, Carbon family, Carbon alloys. 1 A Short History Carbon materials have attracted. (3) typical carbon alloys and their preparation; (4) characterization of carbon alloys; and (5) development and applications of carbon alloys. Prior

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