Solid phase processing of polymers

429 Pages·40.636 MB·English

by  I M Ward, P D Coates, M M Dumoulin, et al

I.M.Ward/P.D.Coates/M.M.Dumoulin
Solid Phase Processing ofPolymers
Polymer Processing Society
Progress in Polymer Processing
Series Editor: L.A. Utracki
A.1.Isayev
Modelingof Polymer Processing
L.A.Utracki
Two-Phase Polymer Systems
A.Singh/J.Silverman
Radiation Processingof Polymers
Series Editor: W.E.Baker
I.Manas-Zloczower/Z.Tadmor
Mixingand Compoundingof Polymers
T.Kanai/G.A.Campbell
Film Processing
R.S.DavejA.C.Loos
Processing of Composites
Series Editor: K.S.Hyun
1.M.Ward/PoD.Coates/M.M.Dumoulin
Solid Phase Processingof Polymers
I.M. Ward/P.D.Coates/M.M.Dumoulin (Editors)
Solid Phase Processing
of Polymers
With Contributions from
A.Ajji, D.C.Bassett, C.W.M.Bastiaansen,
W.Bessey, P.D.Coates, K.C.Cole, M.M.Dumoulin,
M.J.N.Jacobs, M.Jaffe, P.J.Lemstra,J.E.McIntyre,
S.Osawa,T.Peijs, R.S.Porter, J.Sweeny, A.K.Taraiya,
J.-F.Tassin, I.M.Ward.
HANSER
Hanser Publishers, Munich
Hanser Gardner Publications, Inc., Cincinnati
TheEditors:
T.M.Ward. IRCinPolymerScience &Technology,DeptofPhysics& Astronomy,UniversityofLeeds,
LeedsLS29JT,UK
P.D.Coates, IRCinPolymer Science &Technology.DeptofMechanical &ManufacturingEngineering,
UniversityofBradford, BradfordBD7 IDP,UK
M.M.Dumoulin.Industrial Materials Institute,NationalResearchCouncil Canada
75,BoulevarddeMortagne, Boucherville,Quebec, Canada14B6Y4
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Solidphaseprocessing ofpolymers/editedbyI.M.Ward,P.D.Coates, andM.M.Dumoulin
withcontributionsfromA.Ajii... letal).
p.em.
Includesbibliographicalreferencesandindex.
ISBN I-56990-307-7 (hardcover)
I.Plastics-Forming.I.Ward,I.M.(IanMacmillan), 1928-II.Coates, P.D.(PhilD.)III.Dumoulin, M.M.
TPI150.S6652000
668.4'12-dc21 00-039660
DieDeutscheBibliothek- Einheitsaufnahme
Solidphaseprocessing ofpolymers/ed.byI.M.Ward...WithcontributionsfromA.Ajii ...
Munich:Hanser:Cincinnati:HanserGardner,2000
ISBN3-446-19622-6
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PROGRESS IN POLYMER PROCESSING SERIES
Kun Sup Hyun, Series Editor:
EDITORIAL ADVISORY BOARD
Prof. Jean-Francois Agassant Prof. A. I. Isayev
Ecole Nationale Superieure des Mines University ofAkron
de Paris U.S.A.
FRANCE
Prof. Musa Kamal
Dr.Warren Baker McGill University
ATPlastics CANADA
CANADA
Prof. Takeshi Kikutani
Prof. Stephen Bush
Tokyo Institute ofTechnology
UMIST
JAPAN
UNITED KINGDOM
Prof. S. C. Kim
Prof. GregoryCampbell
KoreaAdvanced Institute ofScience and
Clarkson University
Technology
U.S.A.
KOREA
Prof. Hans-GerhardFritz
Prof. P.Lafleur
Institutfur Kunststofftechnologie
Ecole polytechniquede Montreal
Universitat Stuttgart
CANADA
GERMANY
Dr. Hans-Martin Laun
Dr.LloydGoettler
BASF
Consultant
GERMANY
U.S.A.
Prof. Jean-Marc Daudin Prof.ToshiroMasuda
Ecole Nationale Superieuredes Mines Kyoto University
de Paris JAPAN
FRANCE
Prof. WalterMichaeli
Prof. Takashi Inoue Institutfur Kunststoffverarbeitung
Tokyo Institute ofTechnology Aachen
JAPAN GERMANY
Dr.A.Misra Dr.George Vassilatos
lIT - New Delhi E.I. DuPont Co.
INDIA U.S.A.
Dr.Tadamoto Sakai Prof. John Vlachopoulos
Japan Steel Works McMasterUniversity
JAPAN CANADA
Dr.Christine Strohm Prof. I.M.VVard
Hanser Gardner Publications The University ofLeeds
U.S.A. UNITED KINGDOM
Prof. Zehev Tadmor Prof. James L. VVhite
Technion University ofAkron
ISRAEL U.S.A.
Dr.Hideroh Takahashi Prof. XiXu
ToyotaCentral Research and Development Chengdu University ofScience and
LaboratoriesInc. Technology
JAPAN CHINA
Dr.LeszekA.Utracki
National Research Council of Canada
CANADA
VII
Foreword
Since the SecondWorld War,the industry based on polymeric materials has developed ra
pidly and spread widely. The polymerization of new polymeric species advanced rapidly
duringthe sixtiesand the seventies,providingawide rangeofproperties.A plethoraofspe
cialty polymers have followed as well, many with particularly unique characteristics. This
evolution has been invigorated by the implementation ofmetallocene catalyst technology.
The end-use ofthese materials has depended on the development ofnew techniques and
methods for forming, depositing, or locating these materials in advantageous ways, which
are usuallyquite differentfrom those used by the metal or glass fabricating industries.The
importance ofthis activity, "Polymer Processing", is frequently underestimated when re
flecting on the growthand success ofthe industry.
Polymer processes such as extrusion, injection molding, thermoforming, and casting
provide parts and products with specific shapes and sizes. Furthermore, they must control,
beneficially,manyofthe unusualand complex propertiesofthese unique materials. Becau
seoftheirhigh molecularweightsand, in many cases,tendencytocrystallize,polymerpro
cesses are called upon to control the nature and extent oforientation and crystallization,
which intumhave asubstantial influenceonthe final performanceofthe productsmade. In
some cases, these processes involve synthesizing polymers within a classical polymerpro
cessingoperation,suchasreactiveextrusion.Pultrusionand reactioninjectionmoldingboth
synthesize the polymer and form a finished productor part all in one step, evidence of the
maturingofthe industry. For thesereasons,successfulpolymerprocessresearchers and en
gineers must have abroadknowledgeoffundamental principlesand engineering solutions.
Some polymer processes have flourished in large industrial units, synthetic fiber spin
ning for example.Howeverthe bulk ofthe processesare rooted insmall-and mediumsized
entrepreneurial enterprises in both developed and new developing countries. Their energy
and ingenuityhave sustainedgrowth to this pointbut clearlythe future will belongto those
who progressively adapt new scientific knowledge and engineering principles, which can
be appliedto the industry. Mathematical modeling, online processcontroland productmo
nitoring, and characterization based on the latest scientific techniques will be important
tools in keeping these organizationscompetitive in the future.
The Polymer Processing Society was started in Akron, Ohio in 1985 with the aim of
providing a focus, on an international scale, for the development, discussion, and dissemi
nationofnew and improvedpolymerprocessingtechnology. The Society facilitates this by
sponsoring several conferences annually and by publishing the journal International Poly
mer Processing, and the volume seriesProgress in PolymerProcessing.This series oftexts
isdedicatedtothe goal ofbringingtogethertheexpertiseofaccomplishedacademicand in
dustrial professionals. The volumes have a multi-authored format, which provides a broad
picture ofthe volume topic viewed from the perspective ofcontributors from around the
world. To accomplish these goals, we need the thoughtful insight and effort ofour authors
and volume editors, the critical overview ofour Editorial Board, and the efficient produc
tion of our Publisher.
VIII Foreword
This volume deals with the solids phase processingofpolymers for preparing polymer
products, which attain the special mechanical properties due to orientation in the forms of
fibres, films and solid sections including rods, sheets and tubes byspecialfabrication tech
niques. These processes have developed into what is arguably the single largest outlet for
enhancing the properties of synthetic polymers. They are dependent on the best achieve
ments inpolymerdesign to provide theappropriateshearand extensionalviscosityfor suc
cessful processing. These design achievements have also produced the mechanical and op
tical properties so important in applications. Therefore, most important in this volume are
theextensive discussionson thedevelopmentsofmolecularorientationand structuralchan
ges and how these lead to improvements in properties especially mechanical properties.
This volume includes numerous contributions, industrial and academic, from Europe as
well asAsia and North Americaand, as such, forms a very useful contribution to the solid
forming industries. This volume was initiated with Dr.Warren Baker, my predecessorand
becamethe firstvolume I had apleasureto be associated.
Midland, Michigan, KunSupHyun
U.S.A. SeriesEditor
May 2000
IX
Contents
page
1 Introduction
I. M. Ward& P.D. Coates
1.1 Key Scientific Issues I
1.1.1 Thechemicalstructureofthe polymerand its degreesofregularity I
1.1.2 Theeffectofplasticdeformation, the conceptofthe truestress-truestrain 3
curve
1.1.2.1 Startingwithan amorphous or semi-crystallinepolymerand 3
deformingto very highdegrees ofstretch
1.1.2.2 Developmentoforientation in liquidcrystallinepolymers 7
andchain-extendedpolyethylene
1.1.3 Structural considerations: molecularunderstandingofplastic deformation 8
References I0
2 Deformation Mechanisms and Morphology ofCrystallinePolymers
D. C.Bassett
2.1 Introduction II
2.2 MacroscopicPhenomena II
2.3 Cracks, Crazingand Brittleness 12
2.4 Segregation-InducedBrittleness 15
2.5 ColdDrawing 16
2.6 Morphological Factors 17
2.7 MicroscopicObservations 19
2.8 Electron Microscopy 20
2.9 The DeformationofBandedSpherulites 22
2.10 LamellarDeformation 24
2.11 Memory Retention inColdDrawing 25
2.12 OrderingWithin Fibres 27
2.13 Disentanglement 29
2.14 Overview 29
References 30
3 Characterization ofOrientation
K.C.Cole& A. Ajii
3.1 MolecularOrientationand Its Definition 33
3.2 Birefringence 41
3.2.1 Biaxiallyorientedpolyethyleneterephthalate(PET)film 46
3.2.2 PETorientationandrelaxation monitoring 47