Fibers and composites

246 Pages·2003·20.632 MB·English

by  Pierre Delhaes

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
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, ANDX. 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. 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, ANDM. 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
INTRODUCTION TO THE SERIES
The World of Carbonbook 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 Delhaès
January 2003
© 2003 Taylor & Francis
CONTRIBUTORS
X.Bourrat B.Fathollahi
Université de Bordeaux1 Chemical Engineering Program
Laboratoire des Composites Jacobs School of Engineering
Thermo-Structuraux University of California, San Diego
LCTS, 3 Allée La Boëéie La Jolla, CA 92093-0411, USA
F-33 600 Pessac, France e-mail: [email protected]
e-mail: [email protected]
I.Golecki
E.Casal
Corporate R&D Materials Laboratory
Instituto Nacional del Carbón, CSIC
Honeywell International, Inc.
Apartado 73, 33080 Oviedo, Spain
Mail Stop CTC-1, 101 Columbia Road
e-mail: [email protected]
Morristown, NJ 07962, USA
e-mail: [email protected]
D.D.L.Chung
Composite Materials Research Laboratory
University at Buffalo M.Granda
The State University of New York Instituto Nacional del Carbón, CSIC
Buffalo, NY 14260-4400, USA Apartado 73, 33080 Oviedo, Spain
e-mail: [email protected] e-mail: [email protected]
P.Delhaès
K.J.Hüttinger
Centre de recherche Paul Pascal
Institut für Chemische Technik
(CNRS and Université de Bordeaux1)
Kaiserstrasse 12.76128 karlsruhe
33600 Pessac, France
Universität Karlsruhe, Germany
e-mail: [email protected]
e-mail: [email protected]
D.D.Edie
J.-P.Issi
Department of Chemical Engineering and
Unité de Physico-Chimie et de Physique
Center for Advanced Engineering Fibers
des Matériaux
and Films
Université Catholique de Louvain
Clemson University, Clemson
1, Place Croix du Sud, B-1348
South Carolina 29634–0909, USA
Louvain-la-Neuve
e-mail: [email protected]
Belgique
P.Ehrburger e-mail: [email protected]
Université de Haute-Alsace, Laboratoire
Gestion des Risques et Environnement R.Menéndez
25 rue de Chemnitz – 68200 Mulhouse Instituto Nacional del Carbón, CSIC
France Apartado 73, 33080 Oviedo, Spain
e-mail: [email protected] e-mail: [email protected]
© 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: [email protected] USA
© 2003 Taylor & Francis
Part I
CARBON FIBERS
© 2003 Taylor & Francis
1
FORMATION OF MICROSTRUCTURE
IN MESOPHASE CARBON FIBERS
J. L. White†, B. Fathollahi, and X. Bourrat
1 Introduction
Mesophase carbon fiber was invented in the 1970s, independently and simultaneously, from
our viewpoint today, by Leonard Singer in the US (Singer, 1978) and by Sugio Otani in
Japan (Otani, 1981). Both based their concepts on the role of the liquid-crystalline car-
bonaceous mesophase described by Brooks and Taylor in 1965. Both recognized two key
steps: flow of the anisotropic liquid in the shear-stress field of the spinneret to align the disk-
like molecules, and oxidation thermosetting to stabilize the shape and microstructure of the
fiber prior to carbonization.
These inventions led to high expectations in the carbon materials community for the rapid
attainment of fiber with superior properties at the low costs anticipated for a pitch product.
Vigorous research activities ensued, many under conditions of proprietary secrecy. An impor-
tant advance, with potential for many carbon materials besides fiber, was the development of
more satisfactory mesophase pitches, fully transformed to the liquid-crystalline state and of
low viscosity (Lewis and Nazem, 1987; Mochida et al., 1988; Sakanishi et al., 1992).
However for mesophase carbon fiber, the results fell short of expectations. The mechan-
ical properties were not competitive with PAN-based fiber, except for some high-modulus
grades. Low costs were never achieved, apparently due to the lengthy process of stabiliza-
tion and the early 1990’s saw downsizing and abandonment of research programs, with only
a few products commercialized.
Nevertheless the prospects for a carbon fiber spun in the liquid-crystalline state contin-
ued to fascinate carbon scientists. Comprehensive microstructural studies initiated by
Hamada et al. in 1987 demonstrated the remarkable flow memory of viscous mesophase in
a simple spinneret. Then Bourrat et al. (1990a–c) showed that the nanostructure of as-spun
filaments can be described in terms of the basic microstructural features of liquid crystals:
bend, fold, splay, and disclinations.
Some practical results of manipulating the flow of mesophase in the spinneret became
apparent. In a 1990 patent, Hara et al. showed that a fine-weave screen placed across the
mesophase stream flowing to the spinneret can profoundly alter the microstructure of
as-spun fiber. In 1993, Taylor and Cross reported their study of screened flow prior to
spinning; their observations were rationalized in terms of an array of fine mesophase cylin-
ders, leading directly to the concept of a filament comprised of a linear composite of near-
nanotubes. Then rheologists entered the scene to study the flow instabilities of a discotic
liquid crystal under the flow conditions in a spinneret (Singh and Rey, 1995, 1998; Didwania
et al., 1998), thus providing basic guidance for spinning experiments.
†In memorial of Jack White deceased in 2002.
© 2003 Taylor & Francis