FIBERS AND COMPOSITES Edited by Pierre Delhaes Taylor Francis Taylor Francis Group LONDON AND NEW YORK ©2003 Taylor&Francis
FIBERS AND COMPOSITES Edited by Pierre Delhaès © 2003 Taylor & Francis
First published 2003 by Taylor Francis 11 New Fetter Lane.London EC4P 4EE Simultaneously published in the USA and Canada by Taylor Francis Inc, 29 West 35th Street,New York,NY 10001 Taylor Francis is an imprint of the Taylor Francis Group 2003 Taylor Francis Typeset in Times New Roman by Newgen Imaging Systems(P)Ltd,Chennai,India Printed and bound in Great Britain by TJ International Ltd,Padstow,Cornwall All rights reserved.No part of this book may be reprinted or reproduced or utilised in any form or by any electronic,mechanical,or other means,now known or hereafter invented,including photocopying and recording,or in any information storage or retrieval system,without permission in writing from the publishers. Every effort has been made to ensure that the advice and information in this book is true and accurate at the time of going to press.However,neither the publisher nor the authors can accept any legal responsibility or liability for any errors or omissions that may be made.In the case of drug administration,any medical procedure or the use of technical equipment mentioned within this book,you are strongly advised to consult the manufacturer's guidelines. British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library Library of Congress Cataloging in Publication Data A catalog record for this book has been requested ISBN0-415-30826-7 ©2003 Taylor&Francis
First published 2003 by Taylor & Francis 11 New Fetter Lane, London EC4P 4EE Simultaneously published in the USA and Canada by Taylor & Francis Inc, 29 West 35th Street, New York, NY 10001 Taylor & Francis is an imprint of the Taylor & Francis Group © 2003 Taylor & Francis Typeset in Times New Roman by Newgen Imaging Systems (P) Ltd, Chennai, India Printed and bound in Great Britain by TJ International Ltd, Padstow, Cornwall All rights reserved. No part of this book may be reprinted or reproduced or utilised in any form or by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying and recording, or in any information storage or retrieval system, without permission in writing from the publishers. Every effort has been made to ensure that the advice and information in this book is true and accurate at the time of going to press. However, neither the publisher nor the authors can accept any legal responsibility or liability for any errors or omissions that may be made. In the case of drug administration, any medical procedure or the use of technical equipment mentioned within this book, you are strongly advised to consult the manufacturer’s guidelines. British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library Library of Congress Cataloging in Publication Data A catalog record for this book has been requested ISBN 0–415–30826–7 © 2003 Taylor & Francis
CONTENTS Introduction to the series List of contributors PART I Carbon fibers 1 Formation of microstructure in mesophase carbon fibers J.L.WHITE.B.FATHOLLAHI.AND X.BOURRAT Introduction Microstructural approach Manipulation of mesophase flow in a spinneret Discussion 2 The effect of processing on the structure and properties D.D.EDIE Introduction PAN-based carbon fibers Pitch-based carbon fibers New developments Summary Electronic and thermal properties of carbon fibers J.-P.ISSI Introduction Experimental challenges Electrical resistivity Thermal conductivity Thermoelectric power Fibrous intercalation compounds Sample characterization Carbon fiber composites Conclusions ©2003 Taylor&Francis
CONTENTS Introduction to the series List of contributors PART I Carbon fibers 1 Formation of microstructure in mesophase carbon fibers J. L. WHITE, B. FATHOLLAHI, AND X. BOURRAT Introduction Microstructural approach Manipulation of mesophase flow in a spinneret Discussion 2 The effect of processing on the structure and properties D. D. EDIE Introduction PAN-based carbon fibers Pitch-based carbon fibers New developments Summary 3 Electronic and thermal properties of carbon fibers J.-P. ISSI Introduction Experimental challenges Electrical resistivity Thermal conductivity Thermoelectric power Fibrous intercalation compounds Sample characterization Carbon fiber composites Conclusions © 2003 Taylor & Francis
PART II CVD/CVI processes 4 Fundamentals of chemical vapor deposition in hot wall reactors K.J.HOTTINGER Introduction Elementary processes Hydrogen inhibition Surface area/volume ratio Saturation adsorption The role of a complex deposition chemistry for CVI Considerations about the formation of different carbon microstructures Summary Chemical vapor infiltration processes of carbon materials P.DELHAES Introduction General background on CVD and CVI processes CVI processes and efficiency Pyrocarbon microstructures Physical models Carbon-carbon composites Conclusion and outlook 6 Industrial carbon chemical vapor infiltration (CVI)processes I.GOLECKI Introduction Overview of carbon CVI Chemical vapor infiltration processes Summary 7 Liquid impregnation techniques for carbon-carbon composites R.MENENDEZ,E.CASAL,AND M.GRANDA Introduction Impregnation technology Densification efficiency Matrix precursors New developments in C-C composites Summary and conclusions ©2003 Taylor&Francis
PART II CVD/CVI processes 4 Fundamentals of chemical vapor deposition in hot wall reactors K. J. HÜTTINGER Introduction Elementary processes Hydrogen inhibition Surface area/volume ratio Saturation adsorption The role of a complex deposition chemistry for CVI Considerations about the formation of different carbon microstructures Summary 5 Chemical vapor infiltration processes of carbon materials P. DELHAÈS Introduction General background on CVD and CVI processes CVI processes and efficiency Pyrocarbon microstructures Physical models Carbon–carbon composites Conclusion and outlook 6 Industrial carbon chemical vapor infiltration (CVI) processes I. GOLECKI Introduction Overview of carbon CVI Chemical vapor infiltration processes Summary 7 Liquid impregnation techniques for carbon–carbon composites R. MENÉNDEZ, E. CASAL, AND M. GRANDA Introduction Impregnation technology Densification efficiency Matrix precursors New developments in C–C composites Summary and conclusions © 2003 Taylor & Francis
PART III Properties of matrices and composites 8 Structure of pyrocarbons X.BOURRAT Introduction The various pyrocarbons Cones and regenerative features Carbon layer diameter and growth mechanisms Density and anisotropy of pyrocarbons Conclusions 9 Role of chemistry in advanced carbon-based composites C.VIX-GUTERL AND P.EHRBURGER Introduction:principle of composite materials Surface properties of carbon fibers Surface treatment of carbon fibers Carbon fiber reinforced polymers Carbon-carbon composites Carbon-based composites with other matrices Conclusion 10 Carbon-cement composites D.D.L.CHUNG Introduction Structural behavior Thermal behavior Electrical behavior Radio wave reflectivity Cathodic protection of steel reinforcement in concrete Strain sensing Damage sensing Temperature sensing through the thermistor effect Thermoelectric behavior Corrosion resistance Conclusion ©2003 Taylor&Francis
PART III Properties of matrices and composites 8 Structure of pyrocarbons X. BOURRAT Introduction The various pyrocarbons Cones and regenerative features Carbon layer diameter and growth mechanisms Density and anisotropy of pyrocarbons Conclusions 9 Role of chemistry in advanced carbon-based composites C. VIX-GUTERL AND P. EHRBURGER Introduction: principle of composite materials Surface properties of carbon fibers Surface treatment of carbon fibers Carbon fiber reinforced polymers Carbon–carbon composites Carbon-based composites with other matrices Conclusion 10 Carbon–cement composites D. D. L. CHUNG Introduction Structural behavior Thermal behavior Electrical behavior Radio wave reflectivity Cathodic protection of steel reinforcement in concrete Strain sensing Damage sensing Temperature sensing through the thermistor effect Thermoelectric behavior Corrosion resistance Conclusion © 2003 Taylor & Francis
INTRODUCTION TO THE SERIES The World of Carbon book series aims to propose different approaches to carbon materials which summarize the essential information regarding advances and results accumulated in basic and applied research during the last century.Indeed,carbon associated with other atoms is a key element in nature and life.The focus of these books is,however,elemental carbon in a condensed phase,that is,mainly related to materials science. Besides the natural forms of carbon found in earth and in extraterrestrial media,the artificial ones have led to manifold technical applications.They cover areas such as indus- trial chemistry and metallurgy,terrestrial transports as well as aircraft and aeronautics or environmental protection.These examples are related to the numerous old and new forms of carbon that we have partly presented in the first book of the series. The field of research of carbon materials is a beautiful example of the strong interactions between science and technology,where back and forth activity has worked together for a long time.As with other scientific events,a historical approach shows that advances are step-by-step rather than linear with strong breakthroughs;different strata of knowledge are accumulated but sometimes with a loss of memory of the previous one.It is crucial for scientific knowledge,as a part of human activity,that a basic synthesis is realized,which summarized the numerous annual publications.The aim of this series is thus to provide short tutorial articles containing a comprehensive summary of the different topics related to the science of carbon materials.They will be addressed to engineers,scientists and students who are seeking fundamental points whithout"reinventing the wheel". World of Carbon series will be devoted to specific subjects,which cover all forms of carbons:the old ones like graphites or diamonds,but also the applied ones as fibers and composites.Each volume will cover fundamental research in chemistry and physics,as well as current applications and future developments.Such is the case of the second volume, which is devoted to the different forms of fibers,their precursors and their uses.This is one part of the most important industrial applications of graphitic carbons as also carbon blacks, foams and aerogels,insertion and reactivity products.Other polymorphic forms will not be neglected in the future,as carbynes or the new molecular curved forms,fullerenes and nanotubes,which are opening new avenues in nanotechnology. Finally,we expect to present a collection of articles at a level and a style accessible to a large audience that will cover almost all aspects of carbon materials. Pierre Delhaes January 2003 ©2003 Taylor&Francis
INTRODUCTION TO THE SERIES The World of Carbon book series aims to propose different approaches to carbon materials which summarize the essential information regarding advances and results accumulated in basic and applied research during the last century. Indeed, carbon associated with other atoms is a key element in nature and life. The focus of these books is, however, elemental carbon in a condensed phase, that is, mainly related to materials science. Besides the natural forms of carbon found in earth and in extraterrestrial media, the artificial ones have led to manifold technical applications. They cover areas such as industrial chemistry and metallurgy, terrestrial transports as well as aircraft and aeronautics or environmental protection. These examples are related to the numerous old and new forms of carbon that we have partly presented in the first book of the series. The field of research of carbon materials is a beautiful example of the strong interactions between science and technology, where back and forth activity has worked together for a long time. As with other scientific events, a historical approach shows that advances are step-by-step rather than linear with strong breakthroughs; different strata of knowledge are accumulated but sometimes with a loss of memory of the previous one. It is crucial for scientific knowledge, as a part of human activity, that a basic synthesis is realized, which summarized the numerous annual publications. The aim of this series is thus to provide short tutorial articles containing a comprehensive summary of the different topics related to the science of carbon materials. They will be addressed to engineers, scientists and students who are seeking fundamental points whithout “reinventing the wheel”. World of Carbon series will be devoted to specific subjects, which cover all forms of carbons: the old ones like graphites or diamonds, but also the applied ones as fibers and composites. Each volume will cover fundamental research in chemistry and physics, as well as current applications and future developments. Such is the case of the second volume, which is devoted to the different forms of fibers, their precursors and their uses. This is one part of the most important industrial applications of graphitic carbons as also carbon blacks, foams and aerogels, insertion and reactivity products. Other polymorphic forms will not be neglected in the future, as carbynes or the new molecular curved forms, fullerenes and nanotubes, which are opening new avenues in nanotechnology. Finally, we expect to present a collection of articles at a level and a style accessible to a large audience that will cover almost all aspects of carbon materials. Pierre Delhaès January 2003 © 2003 Taylor & Francis
CONTRIBUTORS X.Bourrat B.Fathollahi Universite de Bordeaux1 Chemical Engineering Program Laboratoire des Composites Jacobs School of Engineering Thermo-Structuraux University of California,San Diego LCTS,3 Allee La Boeeie La Jolla.CA 92093-0411.USA F-33 600 Pessac,France e-mail:bfatholl@ucsd.edu e-mail:bourrat@lets.u-bordeaux.fr I.Golecki E.Casal Corporate R&D Materials Laboratory Instituto Nacional del Carbon,CSIC Honeywell International,Inc. Apartado 73,33080 Oviedo,Spain Mail Stop CTC-1,101 Columbia Road e-mail:ecasal@incar.csic.cs Morristown,NJ 07962,USA D.D.L.Chung e-mail:ilan.golecki@honeywell.com Composite Materials Research Laboratory University at Buffalo M.Granda The State University of New York Instituto Nacional del Carbon,CSIC Buffalo,NY 14260-4400,USA Apartado 73,33080 Oviedo,Spain e-mail:ddlchung@aesu.buffals.edu e-mail:mgranda@incar.csic.cs P.Delhaes K.J.Huttinger Centre de recherche Paul Pascal Institut fur Chemische Technik (CNRS and Universite de Bordeaux1) Kaiserstrasse 12.76128 karlsruhe 33600 Pessac,France Universitat Karlsruhe,Germany e-mail:delhaes@crpp.u-bordeaux.fr e-mail:Huettinger@ict.uni-karlsruhe.de D.D.Edie Department of Chemical Engineering and J.-P.Issi Center for Advanced Engineering Fibers Unite de Physico-Chimie et de Physique and Films des Materiaux Clemson University,Clemson Universite Catholique de Louvain South Carolina 29634-0909,USA 1,Place Croix du Sud,B-1348 e-mail:dan.edie@ccs.clemson.edu Louvain-la-Neuve Belgique P.Ehrburger e-mail:issi@pcpm.ucl.ac.bc Universite de Haute-Alsace,Laboratoire Gestion des Risques et Environnement R.Menendez 25 rue de Chemnitz-68200 Mulhouse Instituto Nacional del Carbon,CSIC France Apartado 73,33080 Oviedo,Spain e-mail:P.Ehrburger@uha.fr e-mail:rosmenen@incar.csic.cs ©2003 Taylor&Francis
X. Bourrat Université de Bordeaux1 Laboratoire des Composites Thermo-Structuraux LCTS, 3 Allée La Boëéie F-33 600 Pessac, France e-mail: bourrat@lets.u-bordeaux.fr E. Casal Instituto Nacional del Carbón, CSIC Apartado 73, 33080 Oviedo, Spain e-mail: ecasal@incar.csic.cs D. D. L. Chung Composite Materials Research Laboratory University at Buffalo The State University of New York Buffalo, NY 14260-4400, USA e-mail: ddlchung@aesu.buffals.edu P. Delhaès Centre de recherche Paul Pascal (CNRS and Université de Bordeaux1) 33600 Pessac, France e-mail: delhaes@crpp.u-bordeaux.fr D. D. Edie Department of Chemical Engineering and Center for Advanced Engineering Fibers and Films Clemson University, Clemson South Carolina 29634–0909, USA e-mail: dan.edie@ccs.clemson.edu P. Ehrburger Université de Haute-Alsace, Laboratoire Gestion des Risques et Environnement 25 rue de Chemnitz – 68200 Mulhouse France e-mail: P.Ehrburger@uha.fr B. Fathollahi Chemical Engineering Program Jacobs School of Engineering University of California, San Diego La Jolla, CA 92093-0411, USA e-mail: bfatholl@ucsd.edu I. Golecki Corporate R&D Materials Laboratory Honeywell International, Inc. Mail Stop CTC-1, 101 Columbia Road Morristown, NJ 07962, USA e-mail: ilan.golecki@honeywell.com M. Granda Instituto Nacional del Carbón, CSIC Apartado 73, 33080 Oviedo, Spain e-mail: mgranda@incar.csic.cs K. J. Hüttinger Institut für Chemische Technik Kaiserstrasse 12.76128 karlsruhe Universität Karlsruhe, Germany e-mail: Huettinger@ict.uni-karlsruhe.de J.-P. Issi Unité de Physico-Chimie et de Physique des Matériaux Université Catholique de Louvain 1, Place Croix du Sud, B-1348 Louvain-la-Neuve Belgique e-mail: issi@pcpm.ucl.ac.bc R. Menéndez Instituto Nacional del Carbón, CSIC Apartado 73, 33080 Oviedo, Spain e-mail: rosmenen@incar.csic.cs CONTRIBUTORS © 2003 Taylor & Francis
C.Vix-Guterl J.L.White Institut de Chimie des Surfaces et Chemical Engineering Program Interfaces Jacobs School of Engineering 15 rue Jean Starcky University of California,San Diego 68057 Mulhouse Cedex,France La Jolla,CA 92093-0411 e-mail:C.Vix@uha.fr USA ©2003 Taylor&Francis
C. Vix-Guterl Institut de Chimie des Surfaces et Interfaces 15 rue Jean Starcky 68057 Mulhouse Cedex, France e-mail: C.Vix@uha.fr J. L. White† Chemical Engineering Program Jacobs School of Engineering University of California, San Diego La Jolla, CA 92093-0411 USA © 2003 Taylor & Francis