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Edited by -I - Timothy D. Burchell * Carbon Materials for Advanced Technologies Carbon Materials for Advanced Technologies Edited by Timothy D. Burchell Oak Ridge, National Laboratory Oak Ridge, TN 37831 -6088 U.S.A. 1999 PERGAMON An Imprint of Elsevier Science Amsterdam - Lausanne - New York - Oxford - Shannon - Singapore - Tokyo ELSEVIER SCIENCE Ltd The Boulevard, Langford Lane Kidlington, Oxford 0x5 IGB, UK @ 1999 Elsevier Science Ltd. All rights reserved. This work is protected under copyright by Elsevier science, and the following terms and conditions apply to its use: Photocopying Slngle photocopies of single chapters may be made for personal use as allowed by national copyright laws. Permission of the Publisher and payment of a fee is required for all other photocopying, including multiple or systematic copying, copying for advertising or promotional purposes, resale, and all forms of document delivery. 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Derivative Works Tables of contents may be reproduced for internal circulation, but Permission of Elsevier Science is required for external resale or distribution of such material. Permission of the Publisher is required for all other derivative works, including compilations and translations. Electronic storage or usage Permission of the Publisher is required to store 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 be reproduced, 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 the Publisher. Address permissions requests to: Elsevier Science Rights & Permissions Department, at the mail, fax and e-mail addresses noted above. Notice No responsibility is assumed by the Publisher for any injury and/or damage to persons or property as a matter of Products liability, negligence or otherwise, or from any use or operation of any methods, Products, instructions or ideas contained in the material herein. Because of rapid advances in the medical sciences, in particular, independent verification of diagnoses and drug dosages should be made. First edition 1999 Library of congress Cataloging in Publication Data A catalog record from the 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 0-08-042683-2 @ The paper used in this Publication meets the requirements of ANSI/NISO 239.48-1992 (Permanence of Paper). Printed in The Netherlands. Contents Gon~ibutors xi Acknowledgments xiii pref~ce xv 1 Structure and Bonding in Carbon Materials P Brian Me E naney 1 Introduction 1 2 Crystalline Forms of Carbon 3 3 The Phase and Transition Diagram for Carbon 12 4 CarbonFilms 14 5 Carbon Nanoparticles 18 6 Engineering Carbons 20 7 ConcludingRemarks 28 8 Acknowledgments 29 9 References 29 2 Fullerenes and Nanotubes 39 Mildred S . Dresselhaus . Peter C . Eklund and Gene Dresselhaus 1 Introduction 35 2 4 Applications 84 5 Acknowledgments 87 6 References 87 Fullerenes and Fullerene-based Solids 37 3 Carbon Nanotubes 61 3 Active Carbon Fibers 95 Timothy J. Mays 1 Introduction 95 2 Background 96 3 5 Acknowledgments 111 6 References 111 Applications of Active Carbon Fibers 101 4 ConcludingRemarks 110 vi 4 High Performance Carbon Fibers 119 Dan D . Edie and John J . McHugh Introduction 119 Processing Carbon Fibers from Polyacrylonitrile 119 High Performance Carbon Fibers from Novel Precursors 133 Carbon Fiber Property Comparison 133 Current Areas for High Performance Carbon Fiber Research 134 Summary and Conclusions 135 References 135 Carbon Fibers from Mesophase Pitch 123 5 Vapor Grown Carbon Fiber Composites 139 Max L . Lake and Jyh-Ming Ting Introduction 139 CurrentForms 142 Fiberproperties 144 Composite Properties 146 Potential Applications 158 Manufacturing Issues 160 Conclusions 164 References 165 6 Porous Carbon Fiber-Carbon Binder Composites 169 Timothy D . Burchell Introduction 169 Manufacture 169 Carbon Bonded Carbon Fiber 173 Damage Tolerant Light Absorbing Materials 181 Summary and Conclusions 200 Acknowledgments 201 References 201 Carbon Fiber Composite Molecular Sieves 183 7 Coal-DerivedCarbons 205 Peter G . Stansberry. John W . Zondlo and Alfred H . Stiller 1 Review of Coal Derived Carbons 205 2 SolventExtractionofCoal 211 3 Preparation and Characteristics of Cokes Produced from Solvent Extraction 223 4 Preparation and Evaluation of Graphite from Coal-Derived Feedstocks 229 5 Summary 233 6 Acknowledgments 233 7 References 233 8 Activated Carbon for Automotive Applications 235 Philip J. Johnson. David J. Setsuda and Roger S . Williams Background 235 Activated Carbon 239 Vehicle Fuel Vapor Systems 244 Adsorption 246 Carbon Canister Design 252 Application of Canisters in Running Loss Emission Control 257 Application of Canisters in ORVR Control 263 Summary and Conclusions 265 References 266 9 Adsorbent Storage for Natural Gas Vehicles 269 Terv L . Cook. Costa Komodromos. David F . Quinn and Steve Ragun 1 Introduction 269 2 Storage of Natural Gas 274 3 Adsorbents 280 4 Adsorbent Fill-Empty Testing 293 5 GuardBeds 294 6 Summary 298 7 References 299 [...]... of carbon, C,, or Buclctnmsterfullerene,has been the subject of extensive research, as have the related carbon nanotubes and nanostructures Engineered carbons take many forms For example, cokes, graphites, carbon and graphite fibers, carbon fiber - carbon matrix composites, adsorbent carbons and monoliths, glassy carbons, carbon blacks, carbon films and diamond llke films, Many of these engineered carbon. .. engineers for may years to come References 1 Donnet, J-B and Bansal, R.C Carbon Fibers, 2nd Edition, Marcel Dekker, Inc., New York 1990 2 Thomas, C.R., ed Essentials o Carbon- Carbon Composites,Royal Society of f Chemistry, UK 1993 3 Buckley, J.D and Edie, D.D Carbon- Carbon Materials and Composites, Noyes Publications, Park Ridge, NJ 1993 4 Savage, G Carbon- Carbon Composites, Chapman & Hall, London, 1993 5 D.L... Transformationof the metastable forms to the thermodynamically stable form (i.e., graphite under ambient conditions) is kinetically limited by the high activation energy for the transformation Some carbynoid forms of carbon, e.g., Carbolite [24], may fall into this category, as do amorphous carbon films (see below) 4.1 Amorphous carbon films As noted above, amorphous carbon films can be produced from carboncontaining... metallic forms up to 1.3-2.3 TPa The high pressure-high temperature (up to -2 TPa, 14000 K) phase and transformation diagram for carbon has been reviewed by Sekine [69] 14 4 Carbon Films The transformations between one form of carbon and another can be classified as follows: a) solid-solid transformations, as between diamond and graphite at points 'B' and 'C' in Fig 5; b) solid-solute-solid transformations... of fracture xviii is reported and its performance discussed Clearly, not all forms of carbon material, nor all the possible applications thereof, are discussed in this book However, the application of carbon materials in many advanced technologies are reported here Carbon has played an important role in mankind's technological and social development In the form of charcoal it was an essential ingredient... modulus carbon fibers that enable the lightweight stiff composite structures used in airfiames and spacecraft) Chapter 1 contains a review of carbon materials, and emphasizes the structure and chemical bonding in the various forms of carbon, including the four allotropes diamond, graphite, carbynes, and the fullerenes In addition, amorphous carbon and diamond films, carbon nanoparticles, and engineered carbons... include: (i) crystalline forms of carbon: diamond, graphite, Fullerenes and carbynes; (ii) amorphous carbon films and diamond films; (iii) carbon nanoparticles, including carbon nanotubes; (iv) engineering carbons with moreor-less disordered microstructures based on that of graphite that are the main focus of this book 1,I Bonding between carbon atoms Here, the bonding between carbon atoms is briefly... that the values in Table 1 are mean, overall values Carbon- carbon bond lengths depend upon the local molecular environment Table 2 lists some values of carbon- carbon bond lengths obtained from crystals of organic compounds In general, bond length decreases as the bond order of adjacent carbon- carbon bonds increases Table 1 Some properks of carbon- carbon bonds Bond Bond order Bond length Mean bond enthalpy... The Phase and Transition Diagram for Carbon Elucidation of the phase relationships between the different forms of carbon is a difficult field of study because of the very high temperatures and pressures that must be applied However, the subject is one of great technical importance because of the need to understand methods for transforming graphite and disordered forms of carbon into diamond The diagram... improved adsorbent carbons, advanced cycles, and improved heat transfer in the granular adsorbent carbon beds Chapter 11 reports the use of carbon materials in the fast growing consumer electronics application of lithium-ion batteries The principles of operation of a lithumion battery and the mechanism of Li insertion are reviewed The d u e n c e of the structure of carbon materials on anode performance is . Edited by -I - Timothy D. Burchell * Carbon Materials for Advanced Technologies Carbon Materials for Advanced Technologies Edited. carbynes, and the fullerenes. In addition, amorphous carbon and diamond films, carbon nanoparticles, and engineered carbons are discussed. The most

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