Polymer Morphology: Principles, Characterization, and Processing

472 Pages·2016·27.511 MB·English

by  Qipeng Guo

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POLYMER
MORPHOLOGY
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POLYMER
MORPHOLOGY
Principles, Characterization,
and Processing
Editedby
QIPENGGUO
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LibraryofCongressCataloging-in-PublicationData
Names:Guo,Qipeng,editor.
Title:Polymermorphology:principles,characterization,andprocessing/
editedbyQipengGuo.
Description:Hoboken,NewJersey:JohnWiley&Sons,Inc.,[2016]|Includes
bibliographicalreferencesandindex.
Identifiers:LCCN2015038844(print)|LCCN2015040343(ebook)|ISBN
9781118452158(cloth)|ISBN9781118892763(ePub)|ISBN9781118892770
(AdobePDF)
Subjects:LCSH:Polymers.|Polymerization.|Crystallinepolymers.|Surface
chemistry.
Classification:LCCQD381.9.S97P6252016(print)|LCCQD381.9.S97(ebook)|
DDC547/.7–dc23
LCrecordavailableathttp://lccn.loc.gov/2015038844
Typesetin10/12ptTimesLTStdbySPiGlobal,Chennai,India
PrintedintheUnitedStatesofAmerica
10987654321
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CONTENTS
PREFACE xiii
LISTOFCONTRIBUTORS xv
PARTI PRINCIPLESANDMETHODSOFCHARACTERIZATION 1
1 OverviewandProspectsofPolymerMorphology 3
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JeroldM.Schultz
1.1 IntroductoryRemarks, 3
1.2 ExperimentalAvenuesofMorphologicalResearch, 4
1.2.1 MorphologicalCharacterization:TheEnablingofinsituMeasurements, 4
1.2.2 Morphology–PropertyInvestigation, 5
1.2.3 MorphologyDevelopment, 7
1.3 ModelingandSimulation, 8
1.3.1 Self-GeneratedFields, 9
1.4 WishfulThinking, 11
1.5 Summary, 11
References, 12
2 X-rayDiffractionfromPolymers 14
N.SanjeevaMurthy
2.1 Introduction, 14
2.2 BasicPrinciples, 14
2.3 Instrumentation, 16
2.4 StructureDetermination, 17
2.4.1 LatticeDimensions, 17
2.4.2 MolecularModeling, 18
2.4.3 RietveldMethod, 18
2.4.4 PairDistributionFunctions, 18
2.5 PhaseAnalysis, 19
2.5.1 CrystallinityDetermination, 20
2.5.2 CompositionAnalysis, 21
2.6 CrystalliteSizeandDisorder, 21
2.7 OrientationAnalysis, 22
2.7.1 CrystallineOrientation, 22
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vi CONTENTS
2.7.2 UniaxialOrientation, 22
2.7.3 BiaxialOrientation, 24
2.7.4 AmorphousOrientation, 25
2.8 Small-AngleScattering, 25
2.8.1 CentralDiffuseScattering, 26
2.8.2 DiscreteReflectionsfromLamellarStructures, 27
2.8.3 Small-AngleNeutronScatteringandSolventDiffusion, 29
2.9 SpecializedMeasurements, 30
2.9.1 InsituExperiments, 30
2.9.2 MicrobeamDiffraction, 31
2.9.3 GrazingIncidenceDiffraction, 32
2.10 Summary, 33
References, 33
3 ElectronMicroscopyofPolymers 37
GoergH.MichlerandWernerLebek
3.1 Introduction, 37
3.2 MicroscopicTechniques, 37
3.2.1 ScanningElectronMicroscopy(SEM), 37
3.2.2 TransmissionElectronMicroscopy(TEM), 42
3.2.3 ComparisonofDifferentMicroscopicTechniques, 45
3.2.4 ImageProcessingandImageAnalysis, 46
3.3 SamplePreparation, 47
3.4 InsituMicroscopy, 50
References, 52
(cid:2) 4 CharacterizationofPolymerMorphologybyScatteringTechniques 54 (cid:2)
Jean-MichelGuenet
4.1 Introduction, 54
4.2 AShortTheoreticalPresentation, 55
4.2.1 GeneralExpressions, 55
4.2.2 TheFormFactor, 56
4.3 ExperimentalAspects, 60
4.3.1 TheContrastFactor, 60
4.3.2 ExperimentalSetup, 61
4.4 TypicalResults, 62
4.4.1 NeutronsExperiments:AContrastVariationStory, 62
4.4.2 X-RayExperiments:ATime-ResolvedStory, 67
4.5 ConcludingRemarks, 69
References, 69
5 DifferentialScanningCalorimetryofPolymers 72
AlejandroJ.MüllerandRoseMaryMichell
5.1 IntroductiontoDifferentialScanningCalorimetry.BasicPrinciplesandTypesofDSCEquipment, 72
5.2 DetectionofFirst-OrderandSecond-OrderTransitionsbyDSC.ApplicationsofStandardDSC
ExperimentstotheDeterminationoftheGlassTransitionTemperatureandtheMeltingTemperature
ofPolymericMaterials, 74
5.3 Self-Nucleation, 75
5.3.1 QuantificationoftheNucleationEfficiency, 77
5.4 ThermalFractionation, 78
5.5 MultiphasicMaterials:PolymerBlendsandBlockCopolymers.FractionatedCrystallizationandConfinement
Effects, 81
5.5.1 BlendsandFractionatedCrystallization, 81
5.5.2 Copolymers, 85
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CONTENTS vii
5.5.3 CopolymersVersusBlends, 87
5.5.4 TheCrystallizationofPolymersandCopolymerswithinNanoporousTemplates, 88
5.6 Self-NucleationandtheEfficiencyScaletoEvaluateNucleationPower, 91
5.6.1 Supernucleation, 93
5.7 DeterminationofOverallIsothermalCrystallizationbyDSC, 95
5.8 Conclusions, 95
Acknowledgment, 95
References, 95
6 ImagingPolymerMorphologyusingAtomicForceMicroscopy 100
HolgerSchönherr
6.1 Introduction, 100
6.2 FundamentalAFMTechniques, 101
6.2.1 ContactModeAFM, 101
6.2.2 IntermittentContact(Tapping)ModeAFM, 104
6.2.3 FurtherDynamicAFMModes, 105
6.3 ImagingofPolymerMorphology, 107
6.3.1 SinglePolymerChains, 107
6.3.2 CrystalStructures, 107
6.3.3 LamellarCrystals, 109
6.3.4 Spherulites, 109
6.3.5 MultiphaseSystems, 109
6.3.6 PolymericNanostructures, 111
6.4 PropertyMapping, 113
6.4.1 NanomechanicalProperties, 113
6.4.2 ScanningThermalMicroscopy, 115
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7 FTIRImagingofPolymericMaterials 118
S.G.KazarianandK.L.A.Chan
7.1 Introduction, 118
7.2 PrinciplesofFTIRImaging, 118
7.3 SamplingMethods, 120
7.3.1 TransmissionMode, 120
7.3.2 AttenuatedTotalReflection(ATR)Mode, 121
7.4 SpatialResolution, 122
7.4.1 TransmissionFTIRImaging, 123
7.4.2 ATR–FTIRSpectroscopicImaging, 123
7.5 RecentApplications, 124
7.5.1 PolymerBlends, 124
7.5.2 PolymerProcesses, 125
7.5.3 PolarizedFTIRImagingforOrientationStudies, 126
7.6 Conclusions, 127
References, 128
8 NMRAnalysisofMorphologyandStructureofPolymers 131
TakeshiYamanobeandHirokiUehara
8.1 Introduction, 131
8.2 BasicConceptsinNMR, 131
8.2.1 PrinciplesofNMR, 131
8.2.2 AnalysisoftheFreeInductionDecay(FID), 132
8.3 MorphologyandRelaxationBehaviorofPolyethylene, 134
8.3.1 MorphologyandMolecularMobility, 134
8.3.2 LamellarThickeningbyAnnealing, 134
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8.3.3 EntanglementintheAmorphousPhase, 136
8.4 MorphologyandStructureoftheNascentPowders, 137
8.4.1 EtchingbyFumingNitricAcid, 137
8.4.2 StructuralChangebyAnnealing, 138
8.4.3 NascentIsotacticPolypropylenePowder, 139
8.5 KineticsofDynamicProcessofPolymers, 141
8.5.1 MeltDrawingofPolyethylene, 141
8.5.2 CrystallizationMechanismofNylon46, 143
8.5.3 DegreeofCuringofNovolacResins, 145
8.6 Conclusions, 146
References, 146
PARTII MORPHOLOGY,PROPERTIES,ANDPROCESSING 151
9 Small-AngleX-rayScatteringforMorphologicalAnalysisofSemicrystallinePolymers 153
AnneSeidlitzandThomasThurn-Albrecht
9.1 Introduction, 153
9.2 Small-angleX-rayScattering, 153
9.2.1 TypicalExperimentalSetup, 153
9.2.2 BasicFormalismDescribingtheRelationbetweenReal-SpaceStructureandScatteringIntensityina
SAXSExperiment, 154
9.2.3 MethodsofAnalysisUsedforSAXSonSemicrystallinePolymers, 155
9.3 ConcludingRemarks, 162
Appendix:CalculationoftheModelFunctionK̃′′ (s), 163
sim
References, 163
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10 CrystallineMorphologyofHomopolymersandBlockCopolymers 165
ShuichiNojimaandHironoriMarubayashi
10.1 Introduction, 165
10.2 CrystallineMorphologyofHomopolymers, 165
10.2.1 CrystalStructure, 165
10.2.2 LamellarMorphology, 167
10.2.3 SpheruliteStructure, 168
10.2.4 CrystallineMorphologyofHomopolymersConfinedinIsolatedNanodomains, 168
10.2.5 CrystallineMorphologyofPolymerBlends, 169
10.3 CrystallineMorphologyofBlockCopolymers, 171
10.3.1 CrystallineMorphologyofWeaklySegregatedBlockCopolymers, 172
10.3.2 CrystallineMorphologyofBlockCopolymerswithGlassyAmorphousBlocks, 173
10.3.3 CrystallineMorphologyofStronglySegregatedBlockCopolymers, 174
10.3.4 CrystallineMorphologyofDoubleCrystallineBlockCopolymers, 175
10.4 ConcludingRemarks, 176
References, 176
11 IsothermalCrystallizationKineticsofPolymers 181
AlejandroJ.Müller,RoseMaryMichell,andArnaldoT.Lorenzo
11.1 Introduction, 181
11.2 CrystallizationProcess, 182
11.3 CrystallizationKinetics, 182
11.3.1 TheAvramiEquation[31], 183
11.3.2 NucleationandCrystalGrowth:Lauritzen–HofmannTheory, 188
11.4 IsothermalCrystallizationKinetics–MorphologyRelationship, 191
11.4.1 LinearPS-b-PCLversusMiktoarm(PS )-b-(PCL )BlockCopolymers, 191
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11.4.2 CrystallizationKineticsandMorphologyofPLLA-b-PCLDiblockCopolymers, 194
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