Fundamental Polymer Science (Graduate Texts in Physics)

501 Pages·2019·6.487 MB·English

by  Ulf W. Gedde, Mikael S. Hedenqvist

Graduate Texts in Physics
Ulf W. Gedde
Mikael S. Hedenqvist
Fundamental
Polymer Science
Second Edition
Graduate Texts in Physics
SeriesEditors
KurtH.Becker,NYUPolytechnicSchoolofEngineering,Brooklyn,NY,USA
Jean-Marc Di Meglio, Matie`re et Syste`mes Complexes, B^atiment Condorcet, Universite´ Paris
Diderot,Paris,France
SadriHassani,DepartmentofPhysics,IllinoisStateUniversity,Normal,IL,USA
MortenHjorth-Jensen,DepartmentofPhysics,Blindern,UniversityofOslo,Oslo,Norway
BillMunro,NTTBasicResearchLaboratories,Atsugi,Japan
RichardNeeds,CavendishLaboratory,UniversityofCambridge,Cambridge,UK
William T. Rhodes, Department of Computer and Electrical Engineering and Computer Science,
FloridaAtlanticUniversity,BocaRaton,FL,USA
SusanScott,AustralianNationalUniversity,Acton,Australia
H. Eugene Stanley, Center for Polymer Studies, Physics Department, Boston University, Boston,
MA,USA
MartinStutzmann,WalterSchottkyInstitute,TechnicalUniversityofMunich,Garching,Germany
AndreasWipf,InstituteofTheoreticalPhysics,Friedrich-Schiller-UniversityJena,Jena,Germany
Graduate Texts in Physics
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These textbooks serve students at the MS- or PhD-level and their instructors as comprehensive
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entering,orrequiringtimelyknowledgeof,aresearchfield.
Moreinformationaboutthisseriesathttp://www.springer.com/series/8431
Ulf W. Gedde (cid:129) Mikael S. Hedenqvist
Fundamental Polymer Science
Second Edition
UlfW.Gedde MikaelS.Hedenqvist
FibreandPolymerTechnology FibreandPolymerTechnology
SchoolofEngineeringSciences SchoolofEngineeringSciences
inChemistry,BiotechnologyandHealth inChemistry,BiotechnologyandHealth
KTHRoyalInstituteofTechnology KTHRoyalInstituteofTechnology
Stockholm,Sweden Stockholm,Sweden
ISSN1868-4513 ISSN1868-4521 (electronic)
GraduateTextsinPhysics
ISBN978-3-030-29792-3 ISBN978-3-030-29794-7 (eBook)
https://doi.org/10.1007/978-3-030-29794-7
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Preface
ThisbookhasitsrootsinthetextbookPolymerPhysicsbyUlfGeddepublishedin1995.Theaddition
of a chapter on polymer synthesis and the fact that the chapters labelled “Polymer physics” in fact
contain a substantial part of physical chemistry made us change the book title to Fundamental
Polymer Science. We extend our gratitude to colleagues in our department who have made
contributions to the Polymer Physics book (1995). Maria Conde Bra~na, Kristian Engberg, Anders
Hult,Jan-FredrikJansson,Ha˚kanJonsson,SariLaihonen,FredrikSahle´n,MarieLouiseSkytt,G€oran
Wiberg, Jens Viebke and Bj€orn Terselius. Dr. Richard Jones, Cavendish Laboratory, University of
Cambridge, UK, read through all the chapters and made some very constructive criticisms. Mats
Ifwarson,StudsvikMaterialAB,Sweden;JosefKubat,ChalmersUniversityofTechnology,Sweden;
andAndrewKeller,UniversityofBristol,UK,madecontributionsintheirspecialtyfields.
Fundamental Polymer Science contains 11 chapters discussing the introduction to polymer
science, chain conformation basics, rubber elasticity, polymer solutions including polymer blends,
polymer melts, rheology, liquid crystals, glassy polymers and glass transition, semicrystalline
polymers,crystallizationkinetics,orientedpolymers,polymerchemistryandsolutionstoproblems.
The entire volume has matured with better explanations and more material in general. This comes
naturally,sincewehavebeenteachingthissubjectformanyyearssince1995.Newtopicshavebeen
added. Polysaccharides and proteins are included in essentially all the chapters. One of the keys is
that, regardless of the origin of the polymers, synthetic or native, the same general laws must be
obeyed.Anewadditionisalsopolyelectrolytes.
Eachchapterendswithanumberofproblemsforreaderstosolve.Eachproblemhasasolution,
which is presentedinthefinalchapter.Akeyelement isthat itshould bepossibletoreadthe book
without a very extensive knowledge of mathematics. It presents the basics and finally reaches an
advancedlevel.Thisgivesthebookawiderangeofpossiblereaders:studentsinchemistry,physics,
materialsscience,biotechnologyandcivilengineering.Itissuitableforbothmastersstudents,post-
graduate (doctoral) students and engineers and scientists who have left academia for industry. The
book is rich in illustrations; a picture can tell more than 1000 words. One of the fields which has
expanded during the last decades is simulation and modelling, and, as you will see, many of the
chapterspresentresultsfromthesenon-physicalexperiments.Thebasicideas withineachtopic are
included in the first part of each chapter, and the more novel developments are presented later.
However, not everything can be included. We have therefore many references to more specialized
texts,and,ingeneral,experimentalfindingsarefollowedbyareference.Finally,butnotleast,itmay
be a surprise to readers that we have included a chapter on polymer chemistry, the noble art and
science of how to synthesize polymers. This makes the volume much more complete as a polymer
sciencetextbook.
Many colleagues and fellow scientists are to be thanked: David Bassett, University of Reading,
UK, and Bernard Lotz, Institut Charles Sadron, CNRS, France, for providing fantastic electron
v
vi Preface
micrographs and crystal-clear crystalline polymer physics facts and thoughts; Javier Martinez-
Salazar, Instituto de Estructura de la Materia, CSIC, Spain; Alejandro Mu¨ller, University of the
BasqueCountry,Spain;andGregoryRutledge,MIT,USA,forprovidingdataandinspirationtothe
chapters on crystalline polymer physics, including advanced modelling and simulation; Lars
Wa˚gbergforteachingusaboutpolyelectrolytes;J€orgBaschnagelformakingglassypolymerphysics
more transparent; Maria Skep€o, Lund University, and Joel Markgren, SLU, for valuable inputs and
comments regarding protein physics; Lars Berglund, Mats Johansson, Minna Hakkarainen, Fritjof
NilssonandJakobWohlert,allcolleaguesatourdepartment,whomadevaluableinputsandideasto
manyofthechapters.
Both of us are very grateful to the late Richard H. Boyd, a true gentleman and extraordinary
scientist,whowasourmentorformanyyears.Hewasthefacultyopponentforbothofuswhenwe
defendedourPh.D.theses.Itissadthatheisnolongerwithus,buthisimpactonthisbookispresent.
Neither ofushave English asournative language. We havedependedontwogentlemen,Roger
Brown (the editor of Polymer Testing for many years) and Anthony Bristow, to make the written
languagecorrectandpleasantforyoutoread.AnthonyBristowhasbeenassistingusfor40yearsand
reallyisafantasticpersoncombininglanguageskillandanunderstandingofscienceingeneraland
polymerscienceinparticular.Gedde’syoungerson,SamuelGedde,hasbeenveryefficientinmaking
many of the graphics using Adobe Illustrator. We are very grateful to Maria Bellantone and David
Packer, the publishers at Springer Nature. They have been extremely supportive in the process of
preparingthebook.Davidgaveustheideatoincludeapolymersynthesischapter,whichmadethe
textbookmuchmorecomplete.
HewasalsokeentopromotethewritingofthecompanionvolumewiththetitleAppliedPolymer
Science, consisting of 11 chapters of which four are devoted to experimental methods: thermal
analysis, microscopy, spectroscopy and scattering and chromatography. Simulation and modelling
methods is a field that has become very important; one of the chapters is devoted to this emerging
field. The mechanical and transport properties (diffusion properties) are special to polymers and of
extreme importance and often important parts of student training. They are contained in two of the
chapters. Another chapter is devoted to the processing of polymers into products of various types.
Polymer composites including nanocomposites are treated. The future of polymer engineering
requires that environmental concerns are acknowledged; this is done in a separate chapter. The
chapters end with a problem section; the solution to all the problems is put together in the final
chapter.Thetwovolumescontainmanycross-references.
SeveralreferencesaremadeinthisbookandinthecompanionbookAppliedPolymerScienceto
the textbook Essential Classical Thermodynamics authored by Ulf Gedde. This volume will be
availablein2020,anditisacompactandcomprehensiveaccountofthesubject.
Thepenultimatesectionoftheseacknowledgementsgoestoour‘competitors’,theauthorsofother
textbooksinthisscientificfield.Yourtextshavebeenaninspirationandwehavelearnedfromyou.
The breadth of the whole field is such that, without your guidance, our mission would have been
hopeless.WethereforethankFranciscoBalta´-Calleja,DavidBassett,RichardBoyd,WitoldBrostow,
IanM.Campbell,RalphColby,Pierre-GillesdeGennes,JacquezdesCloizeaux,MasaoDoi,Samuel
Edwards,PaulFlory,JoelR.Fried,PhillipGeil,WilliamGraessley,CharlesHansen,GerardJannink,
HenningKausch,R.Koningsveld,RobertW.Lenz,JamesMark,WayneMattice,GregoryMcKenna,
George Odian, Paul Phillips, Michael Rubinstein, Robert Samuels, Grant Smith, Gert Strobl,
Leendert Struik, Uli Suter, Leslie Treloar, Leszek Utracki, Ian Ward, Alan Windle, Chris G. Vonk
andBernhardWunderlich.Theseauthorshavewrittentextbookswhichhavebeencitedbyus.
Preface vii
WeareindebtedtothestaffatSpringerNaturefortheirpatienceinwaitingforthemanuscriptto
arriveandforperforminganexcellentjobintransformingthemanuscripttothispleasantform.Ms.
ChandhiniKuppusamy,ProductionEditoratSpringerNature,Ms. GopalrajChitra,ProjectManager
atSpi-Globalaregratefullyacknowledgedforbeingsuchacompetentandconstructiveforceinthese
final stages before publication.Weare alsogratefultoourfamiliesRaija andLillifortheir support
duringthewritingprocess.
Stockholm,Sweden UlfW.Gedde
June2019 MikaelS.Hedenqvist
Contents
1 IntroductiontoPolymerScience. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 ThePolymerConceptandtheIntrinsicAnisotropicProperties
ofPolymers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 TheCovalentBond. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.3 SecondaryBonds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.4 ConfigurationandConformation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.5 HomopolymersandCopolymers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.6 MolecularArchitecture. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.7 CommonPolymers:ACollectionofRepeatingUnits
andaLittleAboutThermosets. . .. . . . . . .. . . . . .. . . . . . .. . . . . .. . . . . . .. 14
1.8 MolarMass. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.9 ThermalTransitionsandPhysicalStructure. . . . . . . . . . . . . . . . . . . . . . . . . . . 21
1.10 PolymericMaterials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
1.11 NaturallyExistingPolymers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
1.11.1 Proteins. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
1.11.2 Polysaccharides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
1.12 PolymerHistory. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
1.13 Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
1.14 Exercises. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2 ConformationsinPolymers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
2.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
2.2 MicroscopicViewofConformationalStates. . . . . .. . . . . . .. . . . . .. . . . . . .. 38
2.3 ChainswithPreferredConformation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
2.4 ExperimentalDeterminationoftheDimensionsofChainMolecules. . . . . . . . . 45
2.5 CharacteristicDimensionsofPolymerRandomCoils. . . . . . . . . . . . . . . . . . . . 46
2.6 ModelsforCalculatingtheAverageEnd-to-EndDistance
ofanEnsembleofStatisticalChains. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
2.7 TheEquivalentChain. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
2.8 Worm-likeChains. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
2.9 Random-FlightAnalysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
2.10 ConformationsinProteins. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
2.11 ConformationsinPolysaccharides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
ix
x Contents
2.12 Polyelectrolytes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
2.13 Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
2.14 Exercises. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
3 RubberElasticity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
3.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
3.2 ThermoelasticBehaviourandThermodynamics. . . . . . . . . . . . . . . . . . . . . . . . 78
3.3 TheStatisticalMechanicalTheoryofRubberElasticity. . . . . . . . . . . . . . . . . . 82
3.4 ComparisonofPredictionsMadebyTheoryandExperimentalData. . . . . . . . . 89
3.5 SwellingofRubbersinSolvents. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
3.6 DeviationsfromClassicalStatisticalTheoriesforFinite-Sized
andEntangledNetworks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
3.7 LargeDeformationsWhentheGaussianApproximationIsNotValid. . . . . . . . 98
3.8 A200-YearJourneyPresentingModelsforRubberElasticBehaviour. . . . . . . . 101
3.9 NaturallyExistingElastomers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
3.10 Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
3.11 Exercises. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
4 PolymerSolutions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
4.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
4.2 RegularSolutionModel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
4.3 TheFlory-HugginsTheory. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
4.4 ConcentrationRegimesinPolymerSolutions. . . . . . . . . . . . . . . . . . . . . . . . . . 133
4.5 TheSolubilityParameter. . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . .. . . . . 137
4.6 Equation-of-StateTheories. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
4.7 PolymerBlends. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
4.7.1 AssessmentofMiscibilityofPolymersinBlends. . . . . . . . . . . . . . . . . 145
4.7.2 MiscibilityofPolymersinBlends:PhaseDiagrams
andMolecularInterpretation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
4.8 AggregationinProteinSolutions:TheEgg-WhiteExample. . . . . . . . . . . . . . . 151
4.9 Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
4.10 Exercises. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
5 TheGlassyAmorphousState. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
5.1 IntroductiontoAmorphousPolymers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
5.2 TheGlassTransitionTemperature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
5.2.1 EffectofRepeatingUnitStructureontheGlass
TransitionTemperature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
5.2.2 TheConceptofFreeVolume. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
5.2.3 EffectofMolecularArchitectureontheGlass
TransitionTemperature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
5.2.4 TheGlassTransitionTemperatureofBlends,Copolymers
andwithAddedLowMolarMassCompounds(Plasticizers). . . . . . . . 170
5.2.5 EffectofPressureontheGlassTransitionTemperature. . . . . . . . . . . . 174
5.3 Non-equilibriumFeaturesofGlassyPolymersandPhysicalAging. . . . . . . . . . 174
5.3.1 Phenomenology. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
5.3.2 TheoriesforPhysicalAging. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
5.4 TheWilliams-Landel-Ferry(WLF)Equation. . . . . . . . . . . . . . . . . . . . . . . . . . 184