Epoxy Resins and Composites IV

222 Pages·1986·4.387 MB·English

by  Stephen D. Senturia, Norman F. Sheppard Jr. (auth.), K. Dušek (eds.)

80
Advances in Polymer Science
Epoxy Resins dna
Composites IV
Editor: .K Du~ek
With Contributions by
k1 Dave, M. .P Dudukovi6, H. Furukawa,
.T Kamon, .J L. Kardos, E. .W-.S Kong,
.E E Oleinik, .S .D Senturia, N. E Sheppard, .rJ
With 541 Figures and 91 Tables
galreV-regnirpS Berlin Heidelberg New York
London Pads Tokyo
ISBN-3-540-16423-5 Springer-Verlag Berlin Heidelberg New York
ISBN-0-387-16423-5 Springer-Verlag New York Heidelberg Berlin
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Editors
Prof. William P. Slichter, Chemical Physics Research Department, Bell Tele-
phone Laboratories, Murray Hill, New Jersey 07971, U.S.A.
Prof. John K. StiUe, Department of Chemistry. Colorado State University, Fort
Collins, Colorado 80523, U.S.A.
Editorial
With the publication of Vol. 15 the editors and the publisher
would like to take this opportunity to thank authors and readers
for their collaboration and their efforts to meet the scientific
requirements of this series. We appreciate the concern of our
authors for the progress of "Advances in Polymer Science" and
we also welcome the advice and critical comments of our readers.
With the publication of Vol. 15 we would also like to refer to a
editorial policy: this publishes series invited, critical review articles
of new developments in all areas of polymer science in English
(authors may naturally also include workes of their own). The
responsible editor, that means the editor who has invited the
author, discusses the scope of the review with the author on the
basis of a tentative outline which the author is asked to provide.
The author and editor are responsible for the scientific quality of
the contribution.
Manuscripts must be submitted in content, language and form
satisfactory to Springer-Verlag. Figures and formulas should be
reproducible. To meet the convenience of our readers, the
publisher will include a "volume index" which characterizes the
content of the volume.
The editors and the publisher will make all efforts to publish
the manuscripts as rapidly as possible. Contributions from diverse
areas of polymer science must occasionally be united in one volume.
In such cases a "volume index" cannot meet all expectations, but
will nevertheless provide more information than a mere volume
number.
Starting with Vol. 51, each volume will contain a subject index.
Editors Publisher
Preface
This volume 80 of ADVANCES IN POLYMER SCIENCE
contains the fourth part of a series of critical reviews on selected
topics concerning epoxy resins and composites. The last decade
has been marked by an intense development of applications of
epoxy resins in traditional and newly developing areas such as
coatings, adhesives, civil engineering or electronics and high-
performance composites. The growing interest in applications
and requirements of high quality and performance has provoked
a new wave in fundamental research in the area of resin synthesis,
curing systems, properties of cured products and methods of
their characterization.
The collection of reviews to be published in ADVANCES IN
POLYMER SCIENCE is devoted just to these fundamental
problems. The epoxy resin-curing agent formulations are typical
thermosetting systems of a rather high degree of complexity.
Therefore, some of the formation-structure-properties relationships
are still of empirical or semiempirical nature. The main objective
of this series of articles is to demonstrate the progress in research
towards the understanding of these relationships in terms of
current theories of macromolecular systems.
Because of the complexity of the problems discussed, the
theoretical approaches and interpretation of results presented by
various authors and schools may be somewhat different. It may
be hoped, however, that a confrontation of ideas may positively
contribute to the knowledge about this important class of poly-
meric materials.
In view of the wide range of this volume, it was not possible to
publish all contributions in successive volumes of ADVANCES
IN POLYMER SCIENCE. Part I of the articles is published in
Vol. 72; Part II appeared in Vol. 75 and Part III in Voi. 78.
The reader may appreciate receiving a list of all contributions
to EPOXY RESINS AND COMPOSITES I-IV appearing in
ADVANCES IN POLYMER SCIENCE:
M. T. Aronhime and J. K. Gillham:
The Time-Temperature-Transformation (TTT) Cure Diagram of
Thermosetting Polymeric Systems.
A. Apicella and L. Nicolais (University of Naples, Naples, Italy)
Effect of Water on the Properties of Epoxy Matrix and Composites
(Part I, Vol. 72).
J. M. Barton (Royal Aircraft Establishment, Farnborough, UK):
The Application of Differential Scanning Calorimetry (DSC) to
the Study of Epoxy Resins Curing Reactions (Part I, Vol. 72).
L. T. Drzal (Michigan State University, East Lansing, MI, USA)
The Interphase in Epoxy Composites (Part II, Vol. 75).
K. Du~ek (Institute of Macromolecular Chemistry, Czechoslovak
Academy of Sciences, Prague, Czechoslovakia).
Network Formation in Curing of Epoxy Resins (Part III, Vol. 78).
T. Kamon and H. Furukawa (The Kyoto Municipal Research
Institute of Industry, Kyoto, Japan).
Curing Mechanism and Mechanical Properties of Cured Epoxy
Resins (Part IV, Vol. 80).
J. L. Kardos and M. P. Dudukovi~ (Washington University,
St. Louis. MO, USA).
Void Growth and Transport During Processing of Thermosetting
Matrix Composites (Part IV, Vol. 80).
A. J. Kinloch (Imperial College, London, UK).
Mechanics and Mechanisms of Fracture of Thermosetting Epoxy
Polymers( Part I, Vol. 72).
E. .S W. Kong (Hewlett-Packard Laboratories, Palo Alto, CA,
USA).
Physical Aging in Epoxy Matrices and Composites (Part IV,
Vol. 80).
J. D. LeMay and F. N. Kelley (University of Akron, Akron, OH,
USA).
Structure and Ultimate Properties of Epoxy Resins (Part III,
Vol. 78).
F. Lohse, and H. Zweifel (Ciba-Geigy, Basle, Switzerland).
Photocrosslinking of Epoxy Resins (Part III, Vol. 78).
E. Mertzel and J. L. Koenig (Case Western Reserve University,
Cleveland, OH, USA).
Application of FT-IR and N MR toE poxy Resins (Part II, Vol. 75).
R. J. Morgan (Lawrence Livermore National Laboratory, Liver-
more, CA, USA).
Structure-Properties Relations of Epoxies Used as Composite
Matrices (Part I, Vol. 72).
E. F. Oleinik (Institute of Chemical Physics, Academy of Sciences
of USSR, Moscow, USSR).
Structure and Properties of Epoxy-Aromatic Amine Networks in
the Glassy State (Part IV, Vol. 80).
B. A. Rozenberg (Institute of Chemical Physics, Academy of
Sciences of USSR, Moscow, USSR).
Kinetics, Thermodynamics and Mechanism of Reactions of Epoxy
Oligomers with Amines (Part II, Vol. 75).
.S D. Senturia and N. F. Sheppard (Massachusetts Institute of
Technology,C ambridge, MA, USA).
Dielectric Analysis of Epoxy Cure (Part IV, Vol. .)08
R. G. Schmidt and J. P. Bell (University of Connecticut, Storrs,
CT, USA).
Epoxy Adhesion to Metals (Part II, Vol. .)57
.E M. Yorkgitis, N. .S Eiss, Jr., C. Tran, G. L. Wilkes and J. E.
Mc Grath (Virginia Polytechnic Institute, Blacksburg, VA, USA).
Stloxane Modified Epoxy Resins (Part I, Vol. 72).
The editor wishes to express his gratitude to all contributors for
theicro operation.
Prague, January 6891 Karel Du~ek
Editor
Table of Contents
Dielectric Analysis of Thermoset Cure
S. D. Senturia, N. F. Sheppard, Jr . . . . . . . . . . . .
Epoxy-Aromatic Amine Networks in the Glassy State.
Structure and Properties
E. F. Oleinik . . . . . . . . . . . . . ........ "., 49
Void Growth and Resin Transport During Processing of
Thermosetting -- Matrix Composites
J. L. Kardos, M. P. Dudukovi6, R. Dave . . . . . . . . 101
Physical Aging in Epoxy Matrices and Composites
E. S.-W; Kong . . . . . . . . . . . . . . . . . . . . 125
Curing Mechanisms and Mechanical Properties
of Cured Epoxy Resins
T. Kamon, H. Furukawa . . . . . . . . . . . . . . . 173
Author Index Volumes 1-80 . . . . . . . . . . . . . . 203
Subject Index . . . . . . . . . . . . . . . . . . . . 215
Dielectric Analysis of Thermoset Cure
Stephen D. Senturia
Massachusetts Instituteo f Technology, Cambridge, MA 02139, USA
Norman F. Sheppard, Jr.
Massachusetts Institute of Technology, Cambridge MA 02139, USA
All dielectric measurements involve the determination of the electrical polarization and conduction
properties of a sample subjected to a time-varying electric field. Section 2 addresses dielectric
measurement methods, the various instruments and electrodes, and their calibrations. Section 3 examines
the microscopic mechanisms giving rise in the observed microscopic dielectric properties, and Section 4
explores in detail the effects of temperature and cure on thesper operties. Finally, Section 5 contains a
selected bibliography of applications of dielectric analysis to the study of thermoset cure.
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.1 Historical Perspective . . . . . . . . . . . . . . . . . . . . . . 3
2 Dielectric Measurement Methods . . . . . . . . . . . . . . . . . . . 4
2,1 Admittance Measurements . . . . . . . . . . . . . . . . . . . . 4
2.2 Electrode Geometries and Their Calibrations . . . . . . . . . . . . 8
2.2.1 Definitions . . . . . . . . . . . . . . . . . . . . . . . . 8
2.2.2 Parallel Plate Electrodes . . . . . . . . . . . . . . . . . . . 8
2.2,3 Comb Electrodes . . . . . . . . . . . . . . . . . . . . . . 9
2.2,4 Other Electrodes . . . . . . . . . . . . . . . . . . . . . . 12
2.3 Measurement Equipment . . . . . . . . . . . . . . . . . . . . . 12
2.3.1 Capacitance and Impedance Bridges . . . . . . . . . . . . . 12
2.3.2 Microdielectrometry . . . . . . . . . . . . . . . . . . . . 14
3 Microscopic Mechanisms . . . . . . . . . . . . . . . . . . . . . . . 14
3.1 Bulk Effects . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.1.1 Ionic Conductivity . . . . . . . . . . . . . . . . . . . . . 51
3.1.2 Dipole Orientation . . . . . . . . . . . . . . . . . . . . . 16
3.2 Interface Effects . . . . . . . . . . . . . . . . . . . . . . . . . 20
3.2.1 Electrode Polarization . . . . . . . . . . . . . . . . . . . 20
3.2.2 Blocking and/or Release Layers . . . . . . . . . . . . . . . 23
3.2.3 Fibers and Fillers . . . . . . . . . . . . . . . . . . . . . 24
4 Effects of Temperature and Cure . . . . . . . . . . . . . . . . . . . . 25
4.1 General Issues . . . . . . . . . . . . . . . . . . . . . . . . . 25
4.2 Relation with Chemical Kinetics . . . . . . . . . . . . . . . . . . 28
Advances in Polymer Science 80
© Springer-Verlag Berlin Heidelberg 1986