Physical Properties of Polymers

536 Pages·13.751 MB·English

by  Mark J., Ngai K., Graessley W., Mandelkern L., Samulski E., Koenig J., Wignall G.

PHYSICAL PROPERTIES OF POLYMERS
Thethirdeditionofthiswell-knowntextbookdiscussesthediversephysicalstates
and associated properties of polymeric materials. The contents of the book have
beenconvenientlydividedintotwogeneralparts,“Physicalstatesofpolymers”and
“Somecharacterizationtechniques.”
Thisthirdedition,writtenbysevenleadingfiguresinthepolymer-sciencecom-
munity, has been thoroughly updated and expanded. As in the second edition, all
ofthechapterscontaingeneralintroductorymaterialandcomprehensiveliterature
citationsdesignedtogivenewcomerstothefieldanappreciationofthesubjectand
howitfitsintothegeneralcontextofpolymerscience.
The third edition of Physical Properties of Polymers provides enough core
materialforaone-semestersurveycourseattheadvancedundergraduateorgraduate
level.
Professor James E. Mark is a consultative editor for the Cambridge polymer
sciencelist.

PHYSICAL PROPERTIES
OF POLYMERS
ThirdEdition
JAMES MARK
KIA NGAI
WILLIAM GRAESSLEY
LEO MANDELKERN
EDWARD SAMULSKI
JACK KOENIG
GEORGE WIGNALL
publishedbythepresssyndicateoftheuniversityofcambridge
ThePittBuilding,TrumpingtonStreet,Cambridge,UnitedKingdom
cambridge university press
TheEdinburghBuilding,CambridgeCB22RU,UK
40West20thStreet,NewYork,NY10011–4211,USA
477WilliamstownRoad,PortMelbourne,VIC3207,Australia
RuizdeAlarco´n13,28014Madrid,Spain
DockHouse,TheWaterfront,CapeTown8001,SouthAfrica
http://www.cambridge.org
(cid:1)C JamesMark,KiaNgai,WilliamGraessley,LeoMandelkern,EdwardSamulski,
JackKoenigandGeorgeWignall2003
Thisbookisincopyright.Subjecttostatutoryexception
andtotheprovisionsofrelevantcollectivelicensingagreements,
noreproductionofanypartmaytakeplacewithout
thewrittenpermissionofCambridgeUniversityPress.
PublicationDate2004forthe3rdedition
(cid:1)
1steditionpublished1984AmericanChemicalSociety
(cid:1)
2ndeditionpublished1993byAmericanChemicalSociety–DistributedbyOUP.
PrintedintheUnitedKingdomattheUniversityPress,Cambridge
TypefaceTimes11/14pt SystemLATEX2ε [tb]
AcatalogrecordforthisbookisavailablefromtheBritishLibrary
LibraryofCongressCataloginginPublicationdata
Physicalpropertiesofpolymers/JamesMark...[etal.].–3rdedn.
p. cm.
Includesbibliographicalreferencesandindex
ISBN052182317X–ISBN0521530180(pb.)
1.Polymers.2.Chemistry,Physicalandtheoretical.I.Mark,JamesE.,1934–
TA455.P58P4742003
620.1(cid:2)92–dc21 2003048466
ISBN052182317Xhardback
ISBN0521530180paperback
TheauthorswishtodedicatethisvolumetothememoryofPaulJ.Flory,whose
intuitivegraspofthefundamentalsofpolymersciencepredictedandintegrated
muchoftheresearchdescribedintheirvariouscontributions.Paulwasan
inspiringcolleaguetothoseofuswhowerefortunateenoughtoknowhim,and
onewhoseinfluenceisstillverymuchinevidenceinthefield.

Contents
Notesoncontributors pagex
Preface xv
PartI Physicalstatesofpolymers 1
1 Therubberelasticstate,JamesE.Mark 3
1.1 Introduction 3
1.2 Theory 12
1.3 Someexperimentaldetails 19
1.4 Comparisonsbetweentheoryandexperiment 22
1.5 Someunusualnetworks 31
1.6 Networksatveryhighdeformations 35
1.7 Othertypesofdeformation 46
1.8 Gelcollapse 49
1.9 Energystorageandhysteresis 50
1.10 Bioelastomers 52
1.11 Fillednetworks 54
1.12 Newdevelopmentsinprocessing 60
1.13 Societalaspects 60
1.14 Currentproblemsandnewdirections 60
1.15 Numericalproblems 62
1.16 Solutionstonumericalproblems 62
Acknowledgments 63
References 63
Furtherreading 70
2 Theglasstransitionandtheglassystate,KiaL.Ngai 72
2.1 Introduction 72
2.2 Thephenomenologyoftheglasstransition 75
2.3 Modelsoftheglasstransition 94
vii
viii Contents
2.4 DependencesofT onvariousparameters 101
g
2.5 StructuralrelaxationinpolymersaboveT 114
g
2.6 Theimpactonviscoelasticity 127
2.7 Conclusion 144
Acknowledgments 146
References 146
3 Viscoelasticityandflowinpolymericliquids,
WilliamW.Graessley 153
3.1 Introduction 153
3.2 Conceptsanddefinitions 154
3.3 Linearviscoelasticity 159
3.4 Nonlinearviscoelasticity 170
3.5 Structure–propertyrelationships 184
3.6 Summary 205
References 206
4 Thecrystallinestate,LeoMandelkern 209
4.1 Introduction 209
4.2 Thethermodynamicsofcrystallization–melting
ofhomopolymers 212
4.3 Meltingofcopolymers 217
4.4 Crystallizationkinetics 245
4.5 Structureandmorphology 267
4.6 Properties 295
4.7 Generalconclusions 307
References 308
Furtherreading 315
5 Themesomorphicstate,EdwardT.Samulski 316
5.1 Introduction 316
5.2 Generalconcepts 316
5.3 Monomerliquidcrystals 333
5.4 Macromolecularmesomorphism 353
5.5 Theoriesofmesomorphism 364
Acknowledgment 376
References 376
PartII Somecharacterizationtechniques 381
6 Theapplicationofmolecularspectroscopyto
characterizationofpolymers,JackL.Koenig 383
6.1 Introduction 383
6.2 Vibrationaltechniques 384
Contents ix
6.3 Infraredspectroscopy 387
6.4 Ramanspectroscopy 397
6.5 Nuclear-magnetic-resonancespectroscopy 406
6.6 Massspectroscopy 419
References 422
7 Small-angle-neutron-scatteringcharacterization
ofpolymers,GeorgeD.Wignall 424
7.1 Introduction 424
7.2 Elementsofneutron-scatteringtheory 437
7.3 Contrastanddeuteriumlabeling 444
7.4 SANSinstrumentation 451
7.5 Practicalconsiderations 457
7.6 Someapplicationsofscatteringtechniquestopolymers 468
7.7 Futuredirections 502
Acknowledgments 504
References 504
Index 513