Table Of ContentHANDBOOK OF THERMOSET
PLASTICS
Third Edition
PLASTICSDESIGNLIBRARY(PDL)
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HANDBOOK OF THERMOSET
PLASTICS
Third Edition
Edited by
Hanna Dodiuk
Sidney H. Goodman
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14 15 16 17 18 10 9 8 7 6 5 4 3 2 1
Hanna Dodiuk
To the memory of my late mother, Miriam Auerbach, Shindler’s List and Holocaust
survivor, who taught me to love life in all circumstances.
Sidney H. Goodman
To Rose and Solomon Goodman, who taught me the meaning of scholarship and hard work.
Preface
This third edition contains selected chapters on chemistry is carried out in the supplier site, while in
various thermoset materials, old ones and the most the former case the polymerization andfinal molecu-
novel ones. The final selection of chapters in this lar architecture is controlled in situ by the end user.
edition was based on modern technology and appli- Hence, thermoset technology has an additional
cations as well as novel thermoset chemistry cover- degree of freedom enabling us to design the network
ing many facets of thermoset polymer science and curing density and its derived mechanical as well as
technology as prepared by scientists and experts thermal and physical properties.
hailed from many corners of the globe. Itisdifficulttoimagineanycontemporaryproduct
The science, technology, and applications of ther- used at home, in industry, land transportation, aero-
mosets encompass creativity and imagination, which space,inthemedicalfieldoranywhereelsethatdoes
are common in both science and art, and that serve not use, in some manner, a composite, an adhesive,
as a locomotive to pull forward innovations in tech- asealant,oracoatingbasedonathermosetpolymeric
nology, materials, and products. It is for good reason system. New developments, e.g., chemistry, nano-
thatLeonardodaVinci’sdictum(cid:1)“studythescience technology, encapsulation techniques, have opened
of art and the art of science” (cid:1) is inscribed in one of up new opportunities for incorporation of new ther-
theroomsinLeonardoParkinAmboise,France.The mosetpolymers.
scientist visualizes the mass molecules, studies their Thisthirdeditioncontains18chapters,coveringall
chemical structurebyadvanced spectroscopic means, thermosets resins, from the oldest to the novel ones,
and then changes them according to the particular includingtheirchemistry,properties,andapplications.
functiontheyaremeanttoserve. The structure-process-property relationships are
The advantage of plastics in general and thermo- described followed by relevant examples. The novel
set in particular lies in its wondrous synergy with directions in nanotechnology, the trend in renewable
science, engineering, design, and art. Over the past sources, and new thermosets resins are described in
few years there has been growing interest in quality specificchaptersaswellasnovelprocessingandchar-
plastic ware: plastic has gotten out of the ghetto of acterization methods specifically for thermoset resins.
popular production, and people are inundated with Itshouldbenotedthatthecontentsareverycurrentas
colorful, sophisticated, tactilely pleasing plastic pro- the authors were asked not only to revise but also to
ducts,inprestigiousdesignshopsanddesignexhibi- update their articles according to the latest trends in
tions. Focus on the material itself (cid:1) by developing 2013. Consequently, the chapters in this book offer
means of production,unusualmaterials, andinnova- insight into recent developments and perspectives
tive technologies (cid:1) allows product designers to on many significant ramifications of thermoset
improvefunctionalitemsandmakethemaesthetically polymers science and technology. Hence, this
valuable. text should be of interest to individuals engaged
Extensive research in diverse fields (cid:1) such as and/or interested in the world of thermosets in aca-
industry, architecture, and product design (cid:1) has demia, government research laboratories, a variety
resulted in a more economical use of materials, cou- ofindustries,andotherresearchinstitutes.Thusthe
pled with enhanced functionality. Extensive engineer- value to the engineer, technician, or scientist con-
ing support, including simulations and tests of tinues to be as a comprehensive overview, a place
strength, provides the context for creative solutions to get started and continue in thermoset polymers.
andfacilitatesoriginaldesignconcepts. To those practicing the trade, the new information
Thermoset technology is distinctively different will augment that which is known and offer fresh
from the respective thermoplastic technology. The concepts for consideration as you ponder the solu-
latter is somewhat simple, as the polymerization tiontothenextproblemordesign.
xvii
xviii PREFACE
The 18 chapters written by world-renowned time I was always conscious of thermoset technol-
researchers have been updated as follows: ogy’s significant role in the plastics industry.
After joining the academia (mid 90s) and trying
Chapters 1 and 18: revised introduction and to teach students in Plastics Engineering the chem-
novel processing and characterization methods. istry and properties and curing processes as well
Chapters 2, 3, and 4: revised the amino as well as characterization I found it very difficult since
as the phenol resins and shed light on the new no good textbook existed and most data was either
generations based on polybenzooxazine resins. commercial or kept confidential. The detailed
syntheses as well as resultant chemical structures
Chapters 5, 6, and 7: revised the old and added
were not known. I had to study it in order to be able
novelpolyester,vinylester,allyls,andfuranresins.
to tailor specific properties for specific needs and
Chapters 8 and 9: revised the most popular requirements.
epoxy and polyurethane resins. With time, however, the plastics industry has so
Chapters 10, 11, and 12: cover elevated tempera- burgeoned that its technology and technologists have
ture thermoset resins, polyimides, cyanate esters, elucidated the importance of thermosets. Production
andthenovelmaleimidebasedalder-eneresins. figures continuously define unsaturated polyesters,
urethanes, and epoxies as major commercial entities.
Chapters 13 and 14: revised the silicones as well
The technical base has largely grown, accompanied
as the syntactic foams based thermoset resins.
by significant theoretical understanding of the chem-
Chapters 15 and 16: cover the trend of using
ical processes, manufacturing techniques, and design
renewable sources resins for bio-based thermoset of properties. In short, there is more science and less
resins and summarizes the nanotechnology trends
black magic involved today.
inthefield. Consequently, after three decades of research and
Chapter 17: revised the cross-linking of thermo- development in the industry and academia I felt
plastic resins. thatthiswasthetimetoreviseandrefreshthesecond
edition and to prepare the most updated third edition
I would like to take this opportunity to describe ofthermosetchemistry,processingaswellasapplica-
my personal approach to thermosets polymers. tions. When Elsevier approached me I agreed to take
More than three decades ago, after my Ph.D. and partandtoleadthiseffort.
post-doctoral, I joined the Israel MOD (Ministry Of Although grounded in polymer chemistry and
Defense) research laboratories. My scientific back- science, the papers presented here do not require
ground was physical organic chemistry, especially expertise in these disciplines. It is sufficient for the
photo physical behavior of novel fluorescent probes reader to understand the general principles in the
for biological systems. I had no experience and no introduction i.e., learn the jargon and then can pro-
know-how in thermoset polymers. ceed to any specific chapter for the information
During the first years in the laboratory, I joined sought. Ifthereistobeaconsistentthreadthroughout
the adhesion and encapsulation group where I had eachchapter,itisthatthermosetplasticsarematerials
to study various systems using thermoset adhe- of construction, subject to strengths and weaknesses,
sives, encapsulation resins, and coatings. One of as well as proper use and misuse. The data and
my colleagues made an enthusiastic presentation descriptions presented are for engineers, scientists,
about epoxy. However, when I wondered and technicians, and students who are routinely involved
asked about the exact chemical structure, synthe- and take actions on the basis of informed analysis. It
sis, characterizations, and predicted properties for isourintenttohelpthesereadersmaketherightdeci-
longer times he could not answer me. I began to sions and take the correct actions and thereby avoid
search the literature and the only book I could find thepitfallsourexperiencehasuncovered.
at the beginning of the 80s was the first edition of To each of the contributors, my personal thanks
this Handbook. for their hard work, cooperation, and enthusiasm on
For the first years I worked in nearly all phases this project. I speak for all the contributors in
of thermoset technology, expanding into urethanes, thanking that small ‘army’ of support who helped
taught about phenolic, polyesters, silicones, and with the tough parts: typing, editing, proofreading,
polyimides, and other thermosets. Throughout this offering suggestions: Finally, but no less important,
PREFACE xix
our thanks to Elsevier and their staff for making I hope that the third edition will serve as a guide
order out of chaos and keeping us in full view of for the future in the thermosets’ polymer world.
our final goal.
Prof.HannaDodiuk
My special thanks to Mr. Sidney Goodman for
his great contribution to the thermoset world. The HeadofPolymersandPlasticsEngineering,
PernickFacultyofEngineering,
two previous editions that he edited served for me
ShenkarCollegeofEngineering,
as a guide and textbook for my activity in teaching
DesignandArt,Ramat-Gan,
students as well as my research in the academia
Israel
and industry.
Acknowledgments
First, we are thankful to the officials of Elsevier thorough understanding for this
and especially to Mr. Frank Hellwig for his assis- commitment: my husband and colleague
tance and unwavering help in bringing this book to Prof. Sam Kenig, my dear daughters,
fruition. Lani Dodiuk-Questembert, Attorney at
Our most sincere thanks are extended to the Law, and medical doctor Roni Dodiuk-
authors and reviewers for their contribution, enthusi- Gad, and the joy from my grandchildren,
asm, patience, and cooperation, without which this Jonathan, Coral, and Daria who always
special updated edition would not have been bring a refreshing view of the world.
possible.
Sid: I join Dr. Dodiuk in acknowledging
Finally, as editors of this book we would like to
the efforts of the Elsevier editors and staff
extend very special thanks to our families without
as well as our families and colleagues for
whose help accomplishing of this task would have
their continuing support throughout this
been very difficult ...
project.
To Isao Shimoyama and Abe Landis, my
Hanna: My work on this book would not
close friends and past contributors, I will
have been possible without ongoing
always miss you.
support of my family to whom I am
To Doris, my gratitude for never letting
dedicating this book together with my
me forget how dull my life could have
deepest thanks for their help, when
been.
needed at difficult times and their
xxi
About the Editors
professor at UMASS Lowell, Center for High-Rate
Nanomanufacturing, USA.
Prof. Dodiuk joined Shenkar College of
Engineering and Design in 1997 where she was
appointed the head of Polymers and Plastics
EngineeringDepartmentin2006.
Prof. Dodiuk specializes in the areas of adhesion
and adhesives science and technology, characteriza-
tion and formulation of polymer adhesives, polymer
composites, renewable polymers, biopolymers, den-
drimers and hyperbranched polymers, special coat-
ing (super hydrophobic and super hydrophilic),
surface and interfaces analysis, nanotechnology and
aging of polymeric materials.
Prof. Hanna Dodiuk
Prof. Dodiuk is author and co-author of 130 sci-
entific publications 15 patents and editor of two
Prof. Hanna Dodiuk graduated in 1970, received
books. She delivered numerous (160) lectures and
her MSc in 1973 and PhD in 1977, all with honors,
conference contributions in Europe, USA, Australia
in Chemistry from Tel(cid:1)Aviv University, Israel.
and Japan. Prof. Dodiuk is a member of the
She joined the Israeli Armament Development
Editorial Board of the “International Journal of
Authority (ADA) in 1979. In 1981 was appointed
Adhesion Science and Technology” and “Reviews
as Head of the Adhesion Group in the Materials
of Adhesion and Adhesives”.
and Processes Department.
During 1986(cid:1)1987 she spent a sabbatical year as
a Visiting Professor at the Polytechnic University of
New York, USA, in the Polymer Research Institute. Sidney H. Goodman
Since September 1991 until June 1997 Dr.
Dodiuk held the position of Director of Materials Mr. Goodman received his Bachelor’s Degree in
and Processes Department in ADA. During Chemical Engineering from the University of
1997(cid:1)1999 she spent sabbatical in HPM Company Illinois in 1960. He then was awarded a Master’s
in Los Angeles/US and as a visiting scientist in Degree in Chemical Engineering in 1970 from the
Bayer AG, Leverkusen/Germany. University of Southern California, where he studied
Prof Dodiuk was the president of the Israeli Plastics and Rubber Technology. In 1976 he was
Polymers & Plastics Society during 1998(cid:1)2000 awarded a Lady Davis Fellowship at the Technion,
and was nominated as honorary fellow in 2013. Israel Institute of Technology, in Haifa.
She serves as a representative and expert evaluator Mr. Goodman started his industrial career with
on the European Community’s R&D Grants within Jones Dabney Co., one of the few early manufac-
Frameworks 4(cid:1)7. In 2005 she served as a member turers of epoxy resins and curatives. He later
of Nanotechnology advisory board of Triton moved to California where he worked as a Product
Systems Inc. USA and a visiting Professor in New- Engineer for an epoxy formulator. He then joined
Jersey Institute of Technology, Newark, USA. Applied Plastics Co. where he eventually became
In 2013 she spent short sabbatical as a visiting Plant Manager over the development and
xxiii
