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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

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First edition 1999

Library of congress Cataloging in Publication Data

A catalog record from the Library of Congress has been applied for.

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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

...

vlll

10 Adsorption Refrigerators and Heat Pumps .................... 303

Robert E . Critoph

1

3

4

5

7 References ............................................ 339

Why Adsorption Cycles? ................................. 303

2 The Basic Adsorption Cycle .............................. 306

Basic Cycle Analysis and Results .......................... 313

Choice of Refrigerant . Adsorbent Pairs ..................... 319

Improving Cost Effectiveness ............................. 322

6 Summary and Conclusions ............................... 339

11 Applications of Carbon in Lithium-Ion Batteries ............... 341

Tao Zheng and Jeff Dahn

1 . Introduction ........................................... 341

2 . Useful Characterization Methods ........................... 347

3 . GraphiticCarbons ...................................... 353

4 . Hydrogen-Containing Carbons from Pyrolyzed Organic Precursors 358

5 . Microporous Carbons from Pyrolyzed Hard-Carbon Precursors ... 375

6 . Carbons Used in Commercial Applications ................... 384

7 . References ............................................ 385

12 Fusion Energy Applications ................................. 389

Lance L . Snead

1 . Introduction ........................................... 389

2 .

3 . Irradiation Effects on Thennophysical Properties of Graphite and

Carbon Fiber Composites ................................ 400

4 . Plasma Wall Interactions ................................. 412

5 . Tritium Retention in Graphite ............................. 420

6 . Summary and Conclusions ............................... 424

7 . Acknowledgments ...................................... 424

8 . References ............................................ 425

The Advantages of Carbon as a Plasma-Facing Component ...... 394

ix

13 Fission Reactor Applications of Carbon ....................... 429

Timothy D . Burchell

1 . The Role of Carbon Materials in Fission Reactors ............. 429

2 . Graphite Moderated Power Producing Reactors ............... 438

3 . Radiation Damage in Graphite ............................. 458

4 . RadiolyticOxidation .................................... 469

5 . ............. 473

6 . Summary and Conclusions ............................... 477

7 . Acknowledgments ...................................... 478

8 . References ............................................ 478

Other Applications of Carbon in Fission Reactors

14 Fracture in Graphite ....................................... 485

Glenn R . Romanoski and Timothy D . Burchell

1 .

2 .

3 .

4 .

5 .

6 .

7 .

8 .

9 .

Introduction ........................................... 485

Studies and Models of Fracture Processes in Graphite .......... 486

Linear Elastic Fracture Mechanics Behavior of Graphite ........ 4911

Elastic-plastic Fracture Mechanics Behavior of Graphite ........ 497

Fracture Behavior of Small Flaws in Nuclear Graphites ......... 503

Summary and Conclusions ............................... 530

Acknowledgments ...................................... 531

References ............................................ 532

The Burchell Fracture Model .............................. 515

Index ....................................................... 539

xi

Contributors

Timothy D. Burchell, Metals and Ceramics Division, Oak Ridge National

Laboratory, Oak Ridge, Tennessee 37831, USA

Terry L. Cook, Atlanta Gas Light Company, P.O. Box 4569, Atlanta, Georgia

30302, USA

Robert E. Critoph, Department of Engineering, University of Warwick, Coventry

CV4 7AL, United Kingdom

Jeff Dah, Department of Physics, Dalhousie University, Hulga, Nova Scotia

B3H 3J5, Canada

Gene Dresselhaus, Francis Bitter Magnet Laborato ry, Massachusetts Institute of

Technology, Cambridge, Massachusetts 02139, USA

Mildred S. Dresselhaus, Department of Electrical Engineering and Computer

Science and Department of Physics, Massachusetts Institute of Technology,

Cambridge, Massachusetts 02139, USA

Dan D. Edie, Department of Chemical Engineering, Clemson University,

Clemson, South Carolina 29634, USA

Peter C. Eklund, Department of Physics and Astronomy and Center for Applied

Energy Research, University of Kentucky, Lexington, Kentucky 40506, USA

Philip J. Johnson, Ford Motor Company, Automotive Components Division,

Schaefer Court II, 14555 Rotunda Drive, Dearborn, Michigan 48120, USA

Costa Komodromos, Gas Research Centre, British Gas, Ashby Road,

Loughborough, Leicestershire LEI 1 36U, United Kingdom

Max L. Lake, Applied Sciences, Inc. I41 West Xenia Avenue, Cederville, Ohio

45314, USA

Timothy J. Mays, School of Materials Science and Engineering, University of

Bath, Bath BA2 7AY, United Kingdom

Brian McEnaney, School of Materials Science and Engineering, University of

Bath, Bath BA2 7AY, United Kingdom

John J. McHugh, Hexcel Corporation, Hercules Research Center, Wilmington,

Delaware 19808, USA

David F. Quinn, Royal Military College, Kingston, Ontario K7K 5L0, Canada

Steve Ragan, Sutclifle Speakman Carbons Ltd., Lockett Road, Ashton in

Make@eld, Lancashire wN4 &DE, United Kingdom

Glenn R. Romanoski, Metals and Ceramics Division, Oak Ridge National

Laboratory, Oak Ridge, Tennessee 37831, USA

David J. Setsuda, Ford Motor Company, Automotive Components Division,

Schaefer Court II, 14555 Rotunda Drive, Dearborn, Michigan 48120, USA

Lance L. Snead, Metals and Ceramics Division, Oak Ridge National

Laboratory, Oak Ridge, Tennessee 37831, USA

xii

Peter G. Stansberry, Department of Chemical Engineering, West Virginia

University, Morgantown, West Virginia 26502, USA

Alfred H. Stiller, Department of Chemical Engineering, West Virginia

University, Morgantown, West Virginia 26502, USA

Jyh-Ming Ting, Department of Materials Science and Engineering, National

Cheng Kung Universiv, Tainan, Taiwan

Roger S. Williams, Westvaco Corporation, Washington Street, Covington,

Virginia 24426, USA

Tao Zheng, Department of Physics, Simon Frmer University, Burnaby, British

Columbia VA5 1S6, Canada

John W. Zondlo, Department ofChemica1 Engineering, West Virginia

University, Morgantown, West Virginia 26502, USA

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