Thermal Characterization of Polymeric Materials

976 Pages·1981·16.508 MB·English

by  Edith Turi (Eds.)

Contributors
Harvey E. Bair
P. K. Gallagher
M. Jaffe
Y. P. Khanna
J. J. Maurer
E. M. Pearce
R. Bruce Prime
D. Raucher
Shalaby W. Shalaby
W. W. Wendlandt
Bernhard Wunderlich
Thermal Characterization
of Polymeric Materials
Edited by EDITH A. TURI
Corporate Research and Development
Allied Corporation
Corporate Headquarters
Morristown, New Jersey
1981
ACADEMIC PRESS
A Subsidiary of Harcourt Brace Jovanovich, Publishers
New York London
Paris San Diego San Francisco Sao Paulo
Sydney Tokyo Toronto
Copyright © 1981, by Academic Press, Inc.
ALL RIGHTS RESERVED.
NO PART OF THIS PUBLICATION MAY BE REPRODUCED OR
TRANSMITTED IN ANY FORM OR BY ANY MEANS, ELECTRONIC
OR MECHANICAL, INCLUDING PHOTOCOPY, RECORDING, OR ANY
INFORMATION STORAGE AND RETRIEVAL SYSTEM, WITHOUT
PERMISSION IN WRITING FROM THE PUBLISHER.
ACADEMIC PRESS, INC.
Ill Fifth Avenue, New York, New York 10003
United Kingdom Edition published by
ACADEMIC PRESS, INC. (LONDON) LTD.
24/28 Oval Road, London NW1 7DX
Library of Congress Cataloging in Publication Data
Main entry under title:
Thermal characterization of polymeric materials.
Bibliography: p.
Includes indexes.
1. Polymers and polymerization—Thermal properties.
I. Turi, Edith A.
TA455.P58T5 620.1'9204296 81-17578
ISBN 0-12-703780-2 AACR2
PRINTED IN THE UNITED STATES OF AMERICA
81 82 83 84 9 8 7 6 5 4 3 2 1
List of Contributors
Numbers in parentheses indicate the pages on which the author’s contributions begin.
H arvey E. B air (365, 845), Bell Laboratories, Murray Hill, New Jersey
07974
P. K. Gallagher (1), Bell Laboratories, Murray Hill, New Jersey 07974
M. Jaffe (709), Celanese Research Company, Summit, New Jersey 07901
Y. P. Khanna (793), Corporate Research and Development, Allied Cor­
poration, Morristown, New Jersey 07960
J. J. Maurer (571), Corporate Research Laboratories, Exxon Research
and Engineering Company, Linden, New Jersey 07036
E. M. Pearce (793), Department of Chemistry, Polytechnic Institute of
New York, Brooklyn, New York 11201
R. Bruce Prime (435), International Business Machines Corporation,
San Jose, California 95193
D. Raucher* (793), Department of Chemistry, Polytechnic Institute of
New York, Brooklyn, New York 11201
Shalaby W. Shalaby (235, 365), Research and Development Division,
Ethicon, Inc., Somerville, New Jersey 08876
W. W. Wendlandt (1), Department of Chemistry, University of Hous­
ton, Houston, Texas 77004
Bernhard Wunderlich (91), Department of Chemistry, Rensselaer
Polytechnic Institute, Troy, New York 12181
*Present address: Monsanto Company, St. Louis, Missouri.
IX
Preface
The concept of this book was born of a feeling of frustration I have
shared with many of the scientists engaged in thermal analysis. This was
caused by the lack of a comprehensive reference book covering the very
important field of the thermal characterization of polymers and related
materials.
Polymers, in the past decade, have gained more significance than any
other class of materials. The exponential growth of polymer applications
has led to the development of several new techniques for polymer charac­
terization; no single technique has proved more useful than thermal anal­
ysis. This method delivers information often unobtainable by other means
and has been used in many areas of basic and applied research, produc­
tion, and quality control. New instrumentation, techniques, and applica­
tions have surfaced at an unusual pace; thousands of publications dealing
with thermal analysis in polymer technology appear every year.
My association with national and international societies dedicated to
promoting the theory and application of thermal analysis [such as the
North American Thermal Analysis Society (NATAS) and the Interna­
tional Confederation of Thermal Analysis (ICTA)] presented me with an
opportunity to discuss the idea of this book with prominent scientists in
the field who later agreed to author one or more chapters.
I have designed this book with the objective of presenting a critical
review of the literature and a concise evaluation of the application of ther­
mal analysis in polymer science and engineering. To achieve this goal, I
have asked a team of distinguished authors to undertake the difficult task
of presenting in this volume the state of the art, with proper interpretation
and critical assessment of selected experimental data. In addition, the au­
thors have included many unpublished results of their relevant research.
The authors of this book offer expertise in every area of polymer char­
acterization by thermal analysis. With considerable cooperative effort,
this has been blended into a systematic review that includes the instru­
mentation and the basic principles of thermal analysis, the scientific back­
ground underlying the practical application of thermal analytical tech­
xi
xii Preface
niques, and a large and diversified selection of practical examples for
problem solving. When applicable, nonthermal methods (such as micros­
copy and x-ray diffraction) are also mentioned, since they play a support­
ive role.
This book is to be considered a guideline and not an encyclopedia.
Many of the methods and techniques described in this text may serve as
models for the reader who wants to apply them to some other related
problem. Special efforts were made to keep the references up-to-date;
some of them were added in the last phases of proofreading. Here I wish
to thank the publisher for the flexibility that allowed for these last-minute
additions.
Who benefits from this book? Because of the ever-increasing use of
polymeric materials, more chemists and chemical engineers work in poly-
mer-related fields than in any other single area of industry. The book may
serve as a reference and practical guide for polymer scientists, thermal
analysts, engineers, and technologists. In the libraries of educational in­
stitutions, it will help both teachers and students.
The book provides an in-depth overview of thermal analysis, concen­
trating on the polymer field. The three major parts of the book deal with
instrumentation, theory, and a wide variety of applications.
Instrumentation. The first chapter is a broad treatment of virtually
all aspects of thermal analytical methods and apparatus, with an emphasis
on polymer applications. The present state of the art and the currently
available commercial instruments are described. The subject is treated in
such a way that professionals unfamiliar with the field can quickly gain a
grasp of the techniques while experienced thermal analysts will find a cur­
rent comprehensive treatment complete with suggestions and sources of
value to them.
The Basis of Thermal Analysis. The author of this unique chapter
discusses the theory underlying the basic principles of thermal analysis.
The theories and functions of state for thermometry, dilatometry, thermo­
mechanical analysis, calorimetry, and thermogravimetry are explained.
He describes single-component and multicomponent systems, and their
phase transitions, as influenced by concentration, pressure, deformation,
molecular weight, and copolymerization.
Thermoplastic Polymers. In this section the reader is presented with
an in-depth guide to the important chemical and physical parameters as
they influence the glass transition, crystallization, and melting of thermo­
plastic materials. Factors affecting the thermal and thermo-oxidative deg­
Preface xiii
radations of thermoplastics are also considered. In addition, the chapter
offers a general treatise on the applications of thermal analysis to some
selected problems.
Block Copolymers and Poly blends. This chapter serves as a compre­
hensive review of the applications of the pertinent thermal characteriza­
tion methods. The theoretical aspects of polymer-poly mer compatibility,
phase separation, and miscibility in mixed polymer systems are discussed
in depth. Also stressed is the quantitative analysis based on specific heat
measurements of block and graft copolymers and numerous polyblends.
Thermosets. In Chapter 5 practical applications of thermal analysis
to thermosetting resins (such as epoxies, phenolics, and polyesters) are
stressed. The theoretical and technical backgrounds for the widest range of
applications are provided. The chapter also deals with curing, properties
of uncured resins, cured thermosets, effects of catalysts and fillers, and
other areas of practical importance.
Elastomers. This chapter provides a comprehensive review of the
major thermal methods as applied to elastomers. Screening, develop­
ment, and quality control analysis of practical rubber compounds and vul-
canizates are presented. Both research and development applications of
thermal analysis are covered.
Fibers. A practical approach for obtaining and interpreting thermal
analysis data of fibers is introduced in this chapter. The origin of thermal
analysis responses for fibers is explained from the point of view of prob­
lem solving and polymer physics. The relevance of fiber processing his­
tory to the observed fiber thermal analysis responses is stressed, and
many examples are shown of how thermal history is manifested in the ex­
perimental results.
Thermal Analysis in Polymer Flammability. The authors demon­
strate how thermal analysis techniques can be utilized in the polymer
flammability area. Methods of obtaining information on the relative flam­
mability properties of polymers, for screening fire retardant additives, and
for studying the mechanism of flame inhibition are discussed. Application
of thermal analysis to the flammability of some important polymeric ma­
terials is also covered.
Thermal Analysis of Additives in Polymers. The last chapter is useful
not only in helping the plastics manufacturer develop effective additive
systems for polymers but also in aiding the user to evaluate whether a
polymeric material has the expected processing properties and perfor­
xiv Preface
mance characteristics. The additives that are treated in this chapter include
antioxidants, stabilizers, lubricants, plasticizers, impact modifiers, and
fire retardants.
The intention of this volume was to meet an urgent need and to bridge a
gap between theory and practice. We hope that the users of this work will
find the information and guidance required for achieving their goals in re­
search, production, and application.
The cooperation of the authors in the editorial work was a rewarding
and enjoyable experience. I am most grateful for their invaluable contri­
butions.
The authors of the individual chapters and I have profited greatly from
and appreciate the generous advice and comments of the reviewers.
I wish to express my gratitude to Professor Bernhard Wunderlich for
his helpful suggestions in the various phases of the preparation of this
book. My thanks are also due to a number of publishers and societies for
the courtesy of permitting us to reproduce copyrighted material. My sin­
cere appreciation is expressed to Academic Press for their professional­
ism in the production of this volume, and to the members of their editorial
staff who prepared the Author Index and Subject Index.
Finally, I wish to thank my husband, Paul, a fellow chemist, for sup­
port, guidance, encouragement, and patience during the years of prepara­
tion of this book.
Morristown, New Jersey E dith A. Turi
THERMAL CHARACTERIZATION OF POLYMERIC MATERIALS
CHAPTER 1
Instrumentation
W. W. WENDLANDT
Department of Chemistry
University of Houston
Houston, Texas
P. K. GALLAGHER
Bell Laboratories
Murray Hill, New Jersey
I. Introduction 3
A. Purpose and Scope 3
B. Brief Historical Review 3
II. Thermal Analysis Techniques 6
III. Thermogravimetry—the Thermobalance 9
A. Recording Balances 1 \
B. Sample Containers 13
C. Furnaces and Furnace Temperature Programmers 16
D. Recorders 24
E. Temperature Detection 26
F. Calibration of Furnace Temperature 28
G. Some Potential Sources of Error 32
IV. Commercial Thermobalances 34
A. DuPont Model 951 Thermogravimetric Analyzer 34
B. Perkin-Elmer Model TGS-2 Thermogravimetric System 35
C. Mettler Thermoanalyzer Systems 36
D. Netzsch Thermogravimetric Systems 39
E. Cahn Instruments 40
F. Theta Instruments 41
G. Harrop Laboratories 42
H. Columbia Scientific Industries, Inc. 43
I. SETARAM (Soci6t6 d’Etude d’Automatisation de
Regulation et d’Appareils de Mesures) 43
1
Copyright © 1981 by Academic Press, Inc.
All rights of reproduction in any form reserved.
ISBN 0-12-703780-2
2 W. W. Wendlandt and P. K. Gallagher
J. Shimadzu Thermobalances 43
K. Rigaku TG, TG-DTA, and TG-DSC Systems 44
L. ULVAC-Riko 44
M. Linseis Thermobalances 44
N. Stanton-Redcroft TG-750 Thermobalance 45
O. Hungarian Optical Works (MOM, Budapest) 46
P. Spectrum Products Inc. 46
V. Differential Thermal Analysis (DTA) and Differential Scanning
Calorimetry (DSC) 46
A. Sample Containers 47
B. Differential Temperature Detection Systems 50
C. Furnaces and Furnace Temperature Programmers 53
D. Low-Level de Voltage Amplifiers 56
E. Recorders 56
F. DSC Instruments 56
VI. Commercial DTA and DSC Instruments 60
A. DuPont DSC and DTA Cells 60
B. Perkin-Elmer DSC and DTA 61
C. Mettler DSC and DTA Systems 62
D. Stanton-Redcroft DTA Systems 63
E. Netzsch DSC and DTA Systems 64
F. SETARAM DTA and DSC Systems 64
G. Harrop DTA System 65
H. TECO Thermit 10-C DTA System 65
I. Rigaku Thermoflex DTA and DSC System 66
J. Columbia Scientific Industries DTA and DSC Systems 66
K. Theta DTA Systems 66
L. Linseis Co. DTA and DSC Systems 67
M. Hungarian Optical Works (MOM, Budapest) 67
N. Tetrahedron Associates, Inc. 67
O. ULVAC (Sinku-Riko) DTA and DSC Systems 67
VII. Thermomechanical Analysis (TMA) 68
A. Thermomechanical Analyzers 68
B. DuPont Model 981 Dynamic Mechanical Analysis System 71
C. Polymer Laboratories, Ltd., Dynamic Mechanical Thermal
Analyzer 72
D. Tetrahedron Universal Relaxation Spectrometer 73
E. Torsional Braid Analysis 73
VIII. Evolved Gas Detection and Evolved Gas Analysis 74
IX. Miscellaneous Thermal Analysis Techniques 79
A. Thermosonimetry 79
B. Thermoacoustimetry 80
C. Thermoelectrometry 82
D. Emanation Thermal Analysis (ETA) 83
E. Thermophotometry 83
F. Thermoanalytical Microscopy (TAM) 84
G. Thermal Conductivity and Diffusivity 84
X. Conclusions 85
References 86