Edited by

Vikas Mittal

Characterization Techniques for Polymer Nanocomposites

Polymer Nano-, Micro- & Macrocomposite Series

Mittal, V. (ed.)

Surface Modification of Nanotube FillersSeries: Polymer Nano-, Micro- and Macrocomposites (Volume 1)

2011

ISBN: 978-3-527-32878-9

Mittal, V. (ed.)

In-situ Synthesis of Polymer NanocompositesSeries: Polymer Nano-, Micro- and Macrocomposites (Volume 2)

2012

ISBN: 978-3-527-32879-6

Mittal, V. (ed.)

Modeling and Prediction of Polymer Nanocomposite PropertiesSeries: Polymer Nano-, Micro- and Macrocomposites (Volume 4)

2013

ISBN: 978-3-527-33150-5

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Mittal, V. (ed.)

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Characterization Techniques for Polymer Nanocomposites

Edited by Vikas Mittal

The Editor

Dr. Vikas MittalThe Petroleum InstituteChemical Engineering DepartmentRoom 2204, Bu Hasa BuildingAbu DhabiUAE

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V

Contents

Preface XIII ListofContributors XV

1 CharacterizationofNanocompositeMaterials:AnOverview  1VikasMittal

1.1 Introduction  11.2 CharacterizationofMorphologyandProperties  21.3 ExamplesofCharacterizationTechniques  5

References  12

2 ThermalCharacterizationofFillersandPolymerNanocomposites  13VikasMittal

2.1 Introduction  132.2 TGAofFillers  132.2.1 QuantificationoftheExtentofSurfaceModification  142.2.2 CleanlinessoftheFillerSurface  142.2.3 ComparingtheStabilityofDifferentFillers  152.2.4 DynamicTGAAnalysisoftheFillers  182.2.5 CharacterizationoftheSurfaceReactions  192.2.6 DifferentMeasurementEnvironments  192.2.7 CorrelationofOrganicMatterwithBasalSpacing  222.3 TGAofPolymerNanocomposites  232.3.1 EffectofFillerConcentration  232.3.2 EffectofCompatibilizer  252.4 DSCofFillers  252.4.1 ThermalTransitionsintheModifiedFillers  262.5 DSCofComposites  262.5.1 TransitionsinComposites  262.5.2 OptimizationofCuringConditions  29

References  32

VI Contents

3 Flame-RetardancyCharacterizationofPolymerNanocomposites  33JosephH.Koo,SiChonLao,andJasonC.Lee

3.1 Introduction  333.2 TypesofFlame-RetardantNanoadditives  333.2.1 One-DimensionalNanomaterials  343.2.1.1 MontmorilloniteClay  343.2.1.2 NanographenePlatelets  353.2.2 Two-DimensionalNanomaterials  363.2.2.1 CarbonNanofibers  363.2.2.2 CarbonNanotubes  363.2.2.3 HalloysiteNanotubes  393.2.3 Three-DimensionalNanomaterials  403.2.3.1 Nanosilica  403.2.3.2 Nanoalumina  403.2.3.3 NanomagnesiumHydroxide  403.2.3.4 PolyhedralOligomericSilsequioxanes  413.3 Thermal,Flammability,andSmokeCharacterizationTechniques  423.3.1 IntroductiontoTestMethods  423.3.2 ThermogravimetricAnalysis(TGA)  433.3.3 TheUL94VerticalFlameTest  433.3.4 OxygenIndex(LimitingOxygenIndex)(ASTMD2863-97)  443.3.5 ConeCalorimeter(ASTME1354)  443.3.6 MicroscaleCombustionCalorimeter(ASTMD7309)  453.3.7 SteinerTunnelTest(ASTME84)  453.4 ThermalandFlameRetardancyofPolymerNanocomposites  463.4.1 One-DimensionalNanomaterial-BasedNanocomposites  463.4.1.1 Polymer–ClayNanocomposites  463.4.1.2 Polymer–GrapheneNanocomposites  523.4.2 Two-DimensionalNanomaterial-BasedNanocomposites  543.4.2.1 PolymerCarbonNanofiberNanocomposites  543.4.2.2 PolymerCarbonNanotubeNanocomposites  543.4.2.3 PolymerHalloysiteNanotubeNanocomposites  553.4.3 Three-DimensionalNanomaterial-BasedNanocomposites  573.4.3.1 PolymerNanosilicaNanocomposites  573.4.3.2 PolymerNanoaluminaNanocomposites  573.4.3.3 PolymerNanomagnesiumHydroxideNanocomposites  583.4.3.4 PolymerPOSSNanocomposites  603.4.4 MulticomponentFRSystems:PolymerNanocompositesCombined

withAdditionalMaterials  623.4.4.1 Polymer–ClaywithConventionalFRAdditiveNanocomposites  623.4.4.2 Polymer–CarbonNanotubeswithConventionalFRAdditive

Nanocomposites  633.4.4.3 Polymer–Clayand–CarbonNanotubeswithConventionalFRAdditive

Nanocomposites  643.5 FlameRetardantMechanismsofPolymerNanocomposites  66

Contents VII

3.6 ConcludingRemarksandTrendsofPolymerNanocomposites  68Acknowledgments  69References  69

4 PVTCharacterizationofPolymericNanocomposites  75LeszekA.Utracki

4.1 Introduction  754.2 ComponentsofPolymericNanocomposites  764.2.1 Size,SizeDistribution,andShapeoftheClayPlatelets  774.2.2 ChemicalCompositionofClays  784.2.3 Impurities  794.3 Pressure–Volume–Temperature(PVT)Measurements  794.3.1 Transitions  794.3.2 DeterminationofPVT  804.3.3 EffectsofClay,Intercalant,andCompatibilizer  824.4 Derivatives,Compressibility,andThermalExpansionCoefficient  834.4.1 InterpolatingtheData  834.4.2 ComputationoftheThermalExpansionandCompressibility

Coefficients,αandκ  844.4.3 PolymerαandκfromPVT  844.4.4 EffectofClayonαandκinPS-BasedPNC  864.4.5 EffectofClayonαandκinPA-6BasedPNC  874.5 ThermodynamicTheories  894.5.1 Simha–SomcynskyCell-HoleTheory  904.5.2 Simha–SomcynskyeosforMulticomponentSystems  934.5.3 TheVitreousRegion  974.5.4 EquationofStateforSemicrystallinePNC  984.6 ThermodynamicInteractionCoefficients  1004.7 TheoreticalPredictions  1054.8 SummaryandConclusions  1064.8.1 CharacterizationofClays  1074.8.2 PVTMeasurements  1084.8.3 DerivativeProperties  1084.8.4 ThermodynamicTheories  1084.8.5 InteractionParameters  1094.8.6 TheoreticalPredictions  109

References  109

5 FollowingtheNanocompositesSynthesisbyRamanSpectroscopyandX-RayPhotoelectronSpectroscopy(XPS)  115SorinaAlexandraGareaandHoriaIovu

5.1 NanocompositesBasedonPOSSandPolymerMatrix  1155.1.1 Introduction  1155.1.2 RamanSpectroscopyAppliedforFollowingtheSynthesisof

NanocompositesBasedonPolymerMatrixandPOSS  116

VIII Contents

5.1.3 XPSAppliedforCharacterizationofPolymer-POSSNanocomposites  126

5.1.3.1 AnalysisofFunctionalizedPOSSMolecules  1265.1.3.2 CharacterizationofNanocompositeMaterials  1285.1.4 Conclusions  1285.2 RamanandXPSAppliedinSynthesisofNanocompositesBasedon

CarbonNanotubesandPolymers  1295.2.1 Introduction  1295.2.2 X-RayPhotoelectronSpectroscopy(XPS)UsedtoMonitorizethe

SynthesisofPolymer-CNT-BasedNanocomposites  1305.2.2.1 CNTFunctionalizationwithCarboxylicGroups  1315.2.2.2 CNTFunctionalizationwithAmines  1315.2.2.3 CNTFunctionalizationwithBioconjugatedSystemsBasedon

DendriticPolymersandAntitumoralDrug  1335.2.3 Polymer-CNT-BasedNanocompositesSynthesisFollowedbyRaman

Spectroscopy  1355.2.4 Conclusions  137

Acknowledgments  138References  138

6 TribologicalCharacterizationofPolymerNanocomposites  143MarkusEnglertandAloisK.Schlarb

6.1 Introduction  1436.2 TribologicalFundamentals  1446.2.1 TribologicalSystem  1456.2.2 WearMechanisms  1466.2.3 TransferFilmFormation  1486.2.4 TemperatureIncrease  1486.3 WearExperiments  1496.3.1 SelectedWearModels  1506.3.2 CharacteristicValuesofTribologicalSystems  1506.3.2.1 WearRate  1526.4 SelectionCriteria  1526.5 DesignofPolymerNanocompositesandMultiscale

Composites  1536.6 SelectedExperimentalResults  1536.6.1 ParticulateFillers  1536.6.2 ShortFibers  1556.6.3 CombinationofFillers  1566.6.3.1 InternalLubricantsandShortCarbonFibers  1566.6.3.2 ShortCarbonFibersandNanoparticles  1576.6.4 WearMechanisms  1616.6.4.1 BallBearing(“Rolling”)EffectonaSubmicroScale  1616.6.5 Summary  163

References  165

Contents IX

7 DielectricRelaxationSpectroscopyforPolymerNanocomposites  167ChetanChanmalandJyotiJog

7.1 Introduction  1677.2 TheoryofDielectricRelaxationSpectroscopy  1687.2.1 DielectricRelaxationsinPolymerNanocomposites  1687.2.2 FittingtoExperimentalData  1697.2.3 ActivationEnergyoftheRelaxationProcess  1697.2.4 ModulusFormalism  1707.3 PVDF/ClayNanocomposites  1717.3.1 FrequencyDependenceofDielectricPermittivity  1717.3.2 Vo–ShiModelFittingtoDielectricPermittivity  1727.3.3 RoleofInterface  1737.3.4 FrequencyDependenceofDielectricRelaxationSpectra  1737.4 PVDF/BaTiO3Nanocomposites  1757.4.1 FrequencyDependenceofDielectricRelaxationSpectra  1757.4.2 ElectricModulusPresentationofDielectricRelaxationSpectra  1767.4.3 ActivationEnergyofCrystallineandMWSRelaxation

Processes  1777.5 PVDF/Fe3O4Nanocomposites  1777.5.1 Low-TemperatureDielectricRelaxationSpectra  1787.5.2 ActivationEnergyofGlassTransitionRelaxation  1807.5.3 NormalizedSpectraofDielectricRelaxation  1807.6 ComparativeAnalysisofPVDFNanocomposites  1817.7 Conclusions  182

Acknowledgment  182Nomenclature  182References  183

8 AFMCharacterizationofPolymerNanocomposites  185KenNakajima,DongWang,andToshioNishi

8.1 AtomicForceMicroscope(AFM)  1858.1.1 PrincipleofAFM  1858.1.2 PrincipleofTappingModeAFM  1888.1.3 PhaseandEnergyDissipation  1918.2 ElasticityMeasuredbyAFM  1938.2.1 SampleDeformation  1938.2.2 ContactMechanics  1948.2.3 Sneddon’sElasticContact  1948.2.4 NanopalpationRealizedbyAFM  1978.2.5 AdhesiveContact  1988.2.6 NanomechanicalMapping  2008.3 ExampleStudies  2018.3.1 CarbonNanotubes-ReinforcedElastomerNanocomposites  2018.3.2 InvestigationoftheReactivePolymer–PolymerInterface  2078.3.3 NanomechanicalPropertiesofBlockCopolymers  213

X Contents

8.4 Conclusion  225References  225

9 ElectronParamagneticResonanceandSolid-StateNMRStudiesoftheSurfactantInterphaseinPolymer–ClayNanocomposites  229GunnarJeschke

9.1 Introduction  2299.2 NMR,EPR,andSpinLabelingTechniques  2309.2.1 Solid-StateNMRSpectroscopy  2309.2.2 EPRSpectroscopy  2319.2.3 SpinLabelEPR  2329.2.4 SpinLabelingoftheSurfactantInterphase  2369.3 CharacterizationofOrganicallyModifiedLayeredSilicates  2379.3.1 HeterogeneityofOrganoclays  2379.3.2 HeterogeneityandPositionDependenceofSurfactant

Dynamics  2389.3.3 FurtherFeaturesofSurfactantDynamics  2399.3.4 StructuralAspectsoftheSurfactantLayer  2409.4 CharacterizationofNanocomposites  2429.4.1 IntercalatedNanocompositesandNonintercalatedComposites  2429.4.2 InfluenceofthePolymeronSurfactantDynamics  2439.4.3 InfluenceofthePolymeronSurfactantLayerStructure  2449.5 Conclusion  247

Acknowledgments  248References  248

10 CharacterizationofRheologicalPropertiesofPolymerNanocomposites  251MoSongandJieJin

10.1 Introduction  25110.2 FundamentalRheologicalTheoryforStudyingPolymer

Nanocomposites  25210.3 CharacterizationofRheologicalPropertiesofPolymer

Nanocomposites  25710.4 Conclusions  279

References  280

11 SegmentalDynamicsofPolymersinPolymer/ClayNanocompositesStudiedbySpin-LabelingESR  283YoheiMiwa,ShulamithSchlick,andAndrewR.Drews

11.1 Introduction  28311.2 SpinLabeling:BasicPrinciples  28411.2.1 ESRSpectraofNitroxideRadicals  28411.2.2 LineShapeAnalysisofNitroxideRadicals  28511.3 ExfoliatedPoly(methylacrylate)(PMA)/ClayNanocomposites  286

Contents XI

11.3.1 PreparationofExfoliatedNanocompositesintheAbsenceofSurfactants  286

11.3.2 StructureofExfoliatedNanocomposites  28711.3.3 SegmentalDynamicsofPMAinNanocomposites  28811.3.3.1 TheGlassTransitionTemperature  28811.3.3.2 RestrictedMolecularMotionatthePMA/ClayInterface  28911.3.3.3 ThicknessoftheInterfacialRegion  29111.4 IntercalatedPoly(ethyleneoxide)(PEO)/ClayNanocomposites  29311.4.1 PreparationofIntercalatedPEO/ClayNanocomposites  29311.4.2 StructureofIntercalatedNanocomposites  29411.4.2.1 IntercalationofPEOinClayGalleriesofThickness<1nm  29411.4.2.2 InhibitedCrystallization  29511.4.2.3 DisappearanceoftheGlassTransition  29511.4.2.4 HinderedHydrogenBonding  29611.4.3 SegmentalDynamicsofPEOinClayGalleries  29811.4.3.1 SimulationofESRSpectraandDeterminationofDynamic

Parameters  29811.4.3.2 EffectofGalleryThicknessontheSegmentalMobilityof

IntercalatedPEO  30011.4.3.3 EffectofMolecularWeightontheSegmentalMobilityof

IntercalatedPEO  30011.5 Conclusions  300

Acknowledgments  301References  301

12 CharacterizationofPolymerNanocompositeColloidsbySedimentationAnalysis  303VikasMittal

12.1 Introduction  30312.2 MaterialsandExperimentalMethods  30512.2.1 HybridColloidDispersions  30512.2.2 TurbidityandInterferenceAUC  30512.2.3 StaticDensityGradients  30612.2.4 PreparativeUltracentrifugation  30612.3 ResultsandDiscussion  30712.4 Conclusions  319

Acknowledgments  320References  320

13 BiodegradabilityCharacterizationofPolymerNanocomposites  323KatherineM.Dean,ParveenSangwan,CameronWay,andMelissaA.L.Nikolic

13.1 Introduction  32313.2 MethodsofMeasuringBiodegradation  32313.2.1 AnalyticalTechniques  324

XII Contents

13.2.1.1 Morphological  32413.2.1.2 Microscopic  32413.2.1.3 Gravimetric  32413.2.1.4 PhysicalandThermal  32413.2.1.5 Spectroscopic  32413.2.1.6 Chromatographic  32513.2.1.7 Respirometry  32513.2.2 OxygenDemand  32713.2.3 MicrobiologicalTechniques  32813.2.3.1 DirectCellCount  32813.2.3.2 Clear-Zone  32813.2.3.3 PourPlate/StreakPlate  32913.2.3.4 Turbidity  32913.2.4 EnzymaticTechniques  32913.2.5 MolecularTechniques  32913.3 StandardsforBiodegradation  33113.4 BiodegradableNanocomposites  33113.4.1 PLANanocomposites  33313.5 StarchNanocomposites  33613.6 PCLNanocomposites  33713.7 PHA/PHBNanocomposites  33913.8 NanocompositesofPetrochemical-BasedPolymer  34213.9 Conclusions  343

References  343

Index  347

XIII

Preface

Polymer layered silicate nanocomposites are relatively a new class of nanoscale materials, in which at least one dimension of the filler phase is smaller than 100 nm. They offer an opportunity to explore new behaviors and functionalities beyond that of conventional materials. A large number of advancements have been made in the techniques to modify the filler surface as well as to synthesize the polymer nanocomposites. Such advances need to be supplemented with robust characterization of the resulting composite morphology and properties to gain insights into the various factors affecting the nanocomposite microstructure and properties to be able to design them according to the need. The book summarizes a large number of characterization techniques that have been employed to analyze various aspects of polymer nanocomposites. The aim of the book is also to estab-lish right practices for characterizing the nanocomposite materials with any spe-cific technique.

Chapter 1 provides an overview of the most common characterization tech-niques for the polymer nanocomposites including thermogravimetric analysis, differential scanning calorimetry, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and permeation resistance. Chapter 2 details the thermal characterization of the modified fillers as well as nanocomposites. Correlations of the thermal information with other techniques like X-ray diffrac-tion have also been presented. Chapter 3 focuses on the flame retardancy charac-terization of nanocomposites. Various flame retardants as well as flammability tests have been described in light of a large number of polymer clay nanocompos-ites. PVT characterization of the polymer nanocomposites is described in Chapter 4. The chapter deals with characterization of clays, PVT measurements, derivative properties, thermodynamic theories, interaction parameters, and theoretical predictions. Chapter 5 reports on the nanocomposites synthesis analysis by Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). Both POSS and nanotube-based polymer nanocomposites are reviewed. Tribological characteriza-tion of the nanocomposites is described in Chapter 6. First, the basics of tribology are discussed, followed by the description of possibilities in order to develop tri-bologically optimized nanocomposites. Afterward their characterization by special tribological methods is focused as well as selected results in respect of the tribo-logical properties of nanocomposites. Chapter 7 reports on the use of dielectric

XIV Preface

relaxation spectroscopy for polymer nanocomposites based on poly(vinylidene fluoride) (PVDF). A variety of nanofillers such as clay with platelet structure and functional nanoparticles like BaTiO3 and Fe3O4 is explored. Chapter 8 is devoted to describing how atomic force microscope (AFM) is used to characterize polymer nanocomposites. In particular, a newly developed AFM-based technique is intro-duced to obtain Young’s modulus map for various types of polymeric materials. Electron paramagnetic resonance and solid-state NMR studies of the surfactant interphase in polymer–clay nanocomposites are described in Chapter 9. The infor-mation from NMR and EPR on structure and dynamics of surfactant molecules in OMLS is used to provide a solid foundation for discussion of the more complex interphase behavior in the nanocomposites. Chapter 10 focuses on the rheological characterization of polymer nanocomposites. Basic rheological theories are intro-duced and a brief review of the current status of the understanding of rheological properties of polymer nanocomposites is provided. Chapter 11 reports on the segmental dynamics of polymers in polymer clay nanocomposites studied by spin-labeling electron spin resonance (ESR). This is a powerful technique for discerning properties of specific labeled regions or components in complex systems and can provide information on the dynamics on time scales in the range 10−11–10−7 s.

Chapter 12 reports the characterization of the polymer inorganic hybrid colloidal particles by the use of analytical and preparative ultracentrifugation. Biodegrada-bility characterization of nanocomposites is focused on in Chapter 13. The meth-odologies used to measure and understand biodegradation of nanocomposites are discussed. The standards associated with methods are also described followed by a discussion on the biodegradation of a number of nanocomposites types.

I am grateful to Wiley VCH for their kind acceptance to publish the book. I dedicate this book to my mother for being a constant source of inspiration. I express heartfelt thanks to my wife Preeti for her continuous help in co-editing the book as well as for her ideas to improve the manuscript.

Vikas Mittal

XV

ListofContributors

Chetan ChanmalNational Chemical LaboratoryPolymer Science and Engineering DivisionDr. Homi Bhabha RoadPashanPune, Maharashtra 411008India

Katherine M. DeanCSIRO Materials Science and EngineeringGate 5 Normanby RdClayton, Vic. 3168Australia

Andrew R. DrewsFord Motor CompanyFord Research and Advanced EngineeringMD 3179P.O. Box 2053Dearborn, MI 48121USA

Markus EnglertUniversity of KaiserslauternGottlieb Daimler StrasseGebäude 4467663 KaiserslauternGermany

Sorina Alexandra GareaUniversity Politehnica of BucharestAdvanced Polymer Materials Group149 Calea Victoriei010072 BucharestRomania

Horia IovuUniversity Politehnica of BucharestAdvanced Polymer Materials Group149 Calea Victoriei010072 BucharestRomania

Gunnar JeschkeLab. Phys. Chem.ETH ZürichWolfgang-Pauli-Strasse 108093 ZürichSwitzerland

Jie JinLoughborough UniversityDepartment of MaterialsAshby RoadLoughborough LE11 3TUUK

XVI ListofContributors

Jyoti JogNational Chemical LaboratoryPolymer Science and Engineering DivisionDr. Homi Bhabha RoadPashanPune, Maharashtra 411008India

Joseph H. KooThe University of Texas at AustinDepartment of Mechanical EngineeringTexas Materials InstituteCenter for Nano and Molecular Science and Technology1 University StationC2200Austin, TX 78712-0292USA

Si Chon LaoThe University of Texas at AustinDepartment of Mechanical EngineeringTexas Materials InstituteCenter for Nano and Molecular Science and Technology1 University StationC2200Austin, TX 78712-0292USA

Jason C. LeeInstitute for Soldier NanotechnologiesDepartment of Chemical EngineeringMassachusetts Institute of Technology77 Massachusetts Ave.Cambridge, MA 02139USA

Vikas MittalThe Petroleum InstituteChemical Engineering DepartmentRoom 2204, Bu Hasa BuildingAbu DhabiUnited Arab Emirates

Yohei MiwaUniversity of Detroit MercyDepartment of Chemistry and Biochemistry4001 West McNichols RoadDetroit, MI 48221-3038USA

Ken NakajimaWPI-Advanced Institute forMaterials Research (WPI-AIMR)Tohoku University2-1-1 Katahira, Aoba-ku, SendaiMiyagi 980-8577Japan

Melissa A.L. NikolicCSIRO Materials Science and EngineeringGate 5 Normanby RdClayton, Vic. 3168Australia

Toshio NishiWPI-Advanced Institute forMaterials Research (WPI-AIMR)Tohoku University2-1-1 Katahira, Aoba-ku, SendaiMiyagi 980-8577Japan

ListofContributors XVII

Parveen SangwanCSIRO Materials Science and EngineeringGate 5 Normanby RdClayton, Vic. 3168Australia

Alois K. SchlarbUniversity of KaiserslauternGottlieb Daimler StrasseGebäude 4467663 KaiserslauternGermany

Shulamith SchlickUniversity of Detroit MercyDepartment of Chemistry and Biochemistry4001 West McNichols RoadDetroit, MI 48221-3038USA

Mo SongLoughborough UniversityDepartment of MaterialsAshby RoadLoughborough LE11 3TUUK

Leszek A. UtrackiNational Research Council CanadaIndustrial Materials Institute75 de MortagneBoucherville, QCCanada J4B 6Y4

Dong WangWPI-Advanced Institute forMaterials Research (WPI-AIMR)Tohoku University2-1-1 Katahira, Aoba-ku, SendaiMiyagi 980-8577Japan

Cameron WayCSIRO Materials Science and EngineeringGate 5 Normanby RdClayton, Vic. 3168Australia

1

1

Characterization Techniques for Polymer Nanocomposites, First Edition. Edited by Vikas Mittal.© 2012 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2012 by Wiley-VCH Verlag GmbH & Co. KGaA.

CharacterizationofNanocompositeMaterials:AnOverviewVikasMittal

1.1Introduction

Polymer layered silicate nanocomposites are relatively new class of nanoscale materials, in which at least one dimension of the filler phase is smaller than 100 nm [1–9]. They offer an opportunity to explore new behaviors and functionali-ties beyond that of conventional materials. Owing to nanometer thick platelets in layered silicates, incorporation of such fillers strongly influences the properties of the composites at very low volume fractions because of much smaller interparticle distances and the conversion of a large fraction of the polymer matrix near their surfaces into an interphase of synergistically improved properties. As a result, the desired properties are usually reached at low filler volume fraction, which allows the nanocomposites to retain the macroscopic homogeneity and low density of the polymer.

Montmorillonite has been a layered silicate of choice for most of the studies on polymer nanocomposites. Montmorillonite is an expandable dioctahedral smectite belonging to the family of the 2 : 1 phyllosilicates [10, 11] with a general formula of Mx(Al4−xMgx)Si8O20(OH)4. The particles in montmorillonites consist of stacks of 1 nm thick aluminosilicate layers (or platelets) held electrostatically with each other with a regular gap in between (interlayer). Each layer consists of a central Al-octahedral sheet fused to two tetrahedral silicon sheets. Isomorphic substitutions of aluminum by magnesium in the octahedral sheet generate negative charges, which are compensated for by alkaline-earth or hydrated alkali-metal cations. Based on the extent of the substitutions in the silicate crystals, a term called layer charge density is defined. Montmorillonites have a mean layer charge density of 0.25–0.5 equiv. mol−1. The layer charge is also not constant and can vary from layer to layer; therefore, it should be considered more of an average value. The electro-static and van der Waals forces holding the layers together are relatively weak in smectites and the interlayer distance varies depending on the radius of the cation present and its degree of hydration. As a result, the stacks swell in water and the

2 1 CharacterizationofNanocompositeMaterials:AnOverview

1 nm thick layers can be easily exfoliated by shearing, giving platelets with high aspect ratio. This thus helps to easily exchange their inorganic cations with organic ions (e.g., alkylammonium) to give organically modified montmorillonite (OMMT) [12, 13]. An exchange of inorganic cations with organic cations renders the silicate organophilic and hydrophobic and lowers the surface energy of the platelets and increases the basal-plane or interlayer spacing (d-spacing) [12–16]. This improves the wetting, swelling, and exfoliation of the aluminosilicate in the polymer matrix. Alkyl ammonium ions like octadecyltrimethylammonium, dioctadecyldimethyl-ammonium, etc., have been conventionally used for the organic modification of silicates.

Nanocomposites with practically all the polymer matrices have been reported with varying degrees of property enhancements. Polar polymers have been gener-ally reported to achieve better filler dispersion owing to better match of the surface polarities of filler and polymers. On the other hand, the dispersion of filler in the nonpolar polymers like polyethylene, polypropylene, etc., is challenging owing to the absence of any positive interactions between the organic and inorganic phases. To circumvent these difficulties, either low molecular weight compatibilizers are added to the system or the filler surface is specifically modified by additional chemical or physical processes. The synthesis of nanocomposites has also been reported by a number of different ways, for example, melt compounding, in situ synthesis, solution mixing, gas phase processing, living polymerization, etc. All the different techniques to modify the filler surface as well as to synthesize the polymer nanocomposites need to be supplemented with robust characterization of these processes as well as resulting composite properties to gain insights into the various factors affecting the nanocomposite microstructure and properties so as to be able to design them according to the need.

1.2CharacterizationofMorphologyandProperties

Characterization of the nanocomposite materials is necessary to understand/analyze various facets of polymer nanocomposites. A few of them are listed as follows:

a) quality of dispersion of filler in the polymer matrix along with its orientation or alignment related to the processing method used,

b) effect of filler surface modification on filler dispersion and composite properties,

c) interactions of the filler modification with the polymer chains including chem-ical reactions between the two,

d) changes in the process parameters on the resulting morphology and proper-ties, and

e) apart from that, analysis of a wide spectrum of properties to ascertain the application potential of the nanocomposites.

1.2 CharacterizationofMorphologyandProperties 3

It is also, in many instances, necessary to employ more than one characteriza-tion technique in order to accurately characterize the nanocomposite material. For example, over the years, it has become common to divide the nanocomposites into intercalated and exfoliated types based on the reflections observed in the detection range of wide-angle X-ray diffraction (WAXRD). However, this classifica-tion is arbitrary because the observation of a peak in the diffractogram depends not only on the periodicity but also on other factors, such as the concentration and orientation of the aluminosilicates, and does not exclude the presence of exfoliated part. Its absence also does not exclude the presence of small or randomly oriented intercalated particles and, therefore, does not indicate complete exfolia-tion as often postulated. Figure 1.1 shows an example of polyurethane nanocom-posites generated with montmorillonite filler modified with different surface modifications [17]. The nanocomposites were synthesized by a solution casting method. The X-ray diffractograms of the filler Nanofil 804 (modified with bis(2-hydroxyethyl) hydrogenated tallow ammonium) as well as polyurethane nanocom-posites with different filler volume fractions are shown. The diffraction signals of the filler in the composites were shifted to lower angles confirming the intercalation of the polymer in the interlayers; however, the presence of diffrac-tion peaks also signified that the filler was not exfoliated. The extent of filler intercalation or exfoliation could not be quantified. When the same nanocompos-ites were characterized by transmission electron microscopy as shown in Figure 1.2, extensive filler exfoliation was noticed. The intercalated platelets also had varying thicknesses. Thus, to generate better insights into the nanocomposite microstructures, synergistic combinations of different characterization techniques are useful.

A number of different nanocomposite characterization methods are available which include thermogravimetric analysis, differential scanning calorimetry,

Figure1.1 X-ray diffractograms of the Nanofil 804 filler as well as polyurethane nanocompos-ites with different filler volume fractions. Reproduced from reference [17] with permission from American Chemical Society.

4 1 CharacterizationofNanocompositeMaterials:AnOverview

transmission electron microscopy, scanning electron microscopy, X-ray diffrac-tion, nuclear magnetic resonance, IR spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, dielectric relaxation spectroscopy, atomic force microscopy, electron spin resonance, continuous-wave and pulsed ESR spectros-copy, etc. Apart from that, numerous characterization techniques to ascertain nanocomposite properties like mechanical performance, fire behavior, barrier performance, biodegradability, rheological properties, PVT characterization, tribo-

Figure1.2 TEM micrographs of the 2.86 vol% Nanofil 804-PU composite. Reproduced from reference [17] with permission from American Chemical Society.

1.3 ExamplesofCharacterizationTechniques 5

logical behavior, etc., are also used. The following section shows the overview examples of nanocomposite characterization performed with a few of these tech-niques; however, this section is not meant to be exhaustive.

1.3ExamplesofCharacterizationTechniques

Figure 1.3 [18] shows an example of thermogravimetric analysis (TGA) of the modified fillers. The characterization was carried out to ascertain the filler surface cleanliness so as to use them in high-temperature compounding or in in situ

Figure1.3 TGA thermograms of the (a) commercially modified BzC16; (b) self-treated BzC16; (c) commercially modified 2C18, and (d) self-treated 2C18. Reproduced from reference [18] with permission from Springer.

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6 1 CharacterizationofNanocompositeMaterials:AnOverview

polymerization processes. Fillers modified with sioctadecyldimethylammonium chloride (2C18) and benzylhexadecyldimethylammonium chloride (BzC16) were analyzed. As can be observed, the commercially treated fillers had an additional low-temperature degradation peak, which indicated the presence of excess surface modification molecules in the filler interlayers which were not ionically attached to the filler surface, but were physically trapped in the modification monolayers, thus forming pseudo bilayers. On the other hand, the self-treated fillers were free from any such excess molecules as no low-temperature degradation signal was observed in their thermograms.

Figure 1.4 shows an example of differential scanning calorimetry (DSC) char-acterization of pure polymer to generate information on the melting and crystal-lization transitions as well as to obtain information on the extent of crystallinity from the area under the melting transition (melt enthalpy). The nanocomposite materials can be similarly analyzed to know the effect of fillers on the crystalliza-tion behavior of the pure polymer. The organically modified fillers are also char-acterized by DSC in order to obtain information on the phase dynamics and transitions associated with the monolayers present on the filler surface.

Figure 1.5 [19] presents the WAXRD patterns of octadecytrimethylammonium (C18), dioctadecyldimethylammonium (2C18), and trioctadecylmethylammonium (3C18) modified fillers and their 3 vol% polypropylene nanocomposites. The analy-sis is used to ascertain the increase in interlayer spacing of the fillers after com-

Figure1.4 DSC thermograms of polypropylene using heating rate of 10 °C min−1 and cooling rate of (A) 10 °C min−1 and (B) 40 °C min−1.

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1.3 ExamplesofCharacterizationTechniques 7

pounding with polymers, which is related to the shifting of the diffraction peaks to lower diffraction angles. However, as mentioned earlier, the method does not provide quantification of the extent of intercalation and exfoliation. The filler in the composites in Figure 1.5 was observed to have similar basal plane spacing (as minimal shift in the diffraction peak angle) as the filler powders indicating no intercalation, but the tactoid thickness was observed to be decreased in the micro-scopy analysis and a partial exfoliation of the filler was achieved. The peak intensity in the diffractograms is also not an accurate indication of the extent of intercalation

Figure1.5 Wide angle X-ray diffractograms of (a) 1-3C18 ammonium modified fillers and (b) their PP nanocomposites. Reproduced from reference [19] with permission from Sage Publishers.

8 1 CharacterizationofNanocompositeMaterials:AnOverview

as it depends on other factors like filler concentration, filler orientation, defects in the crystal, and sample preparation methods, etc. Small-angle X-ray analysis is also carried out to analyze the materials in a very low diffraction angle range, which is not possible in the wide-angle X-ray techniques.

Microscopy is commonly used to complement the findings from X-ray diffrac-tion. Figures 1.6 and 1.7 show the scanning and transmission electron microscopy analysis of polymer nanocomposites [19, 20]. It should be noted that the filler

Figure1.6 SEM micrographs of 3 vol% 2C18 modified filler-PP nanocomposites. The filler platelets are visible in different orientation states. Reproduced from reference [19] with permission from Sage Publishers.

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1.3 ExamplesofCharacterizationTechniques 9

platelets are generally observed to be randomly aligned. Apart from misalignment, the platelets are also occasionally bent and folded. The particles of different thick-nesses also indicate that varying degrees of polymer intercalation in the filler interlayers takes place.

Similarly, out of a number of techniques available for characterization of func-tional properties of nanocomposites, two examples of gas barrier property and mechanical property characterization are shown in Figures 1.8 and 1.9, respectively

Figure1.7 TEM micrographs of the 3.5 vol% BzC16 filler – epoxy nanocomposite. The dark lines are cross-sections of aluminosilicate layers. Reproduced from reference [20] with permission from American Chemical Society.

10 1 CharacterizationofNanocompositeMaterials:AnOverview

[17, 21]. The oxygen permeation of the polyurethane nanocomposites as shown in Figure 1.8 is an interesting example as out of the three different fillers, two caused a decrease in oxygen permeation through the polymer, whereas the third filler led to an increase in the oxygen permeation as a function of filler volume fraction. The filler that led to an increase in the permeation was observed to have a least increase in the basal lane spacing as compared to the other two fillers. Also, the microscopy analysis had revealed minimum filler exfoliation in this case. Thus, such microstructure characterizations of the system could also be related to the resulting properties of the nanocomposites. In the example of the mechanical property characterization shown in Figure 1.9 for polypropylene nanocomposites generated with imidazolium modified filler, tensile modulus was observed to increase as a function of filler content, whereas the yield stress was observed to decrease. It indicated that though the load transfer from the polymer chains to the filler particles could take place resulting in an increase in modulus, the filler was still partially exfoliated and the thicker filler tactoids led to reduction in yield stress, which also corresponded with the microscopic characterization of the morphology which was partially exfoliated.

Figure1.8 Dependence of the oxygen transmission rate through the PU-nanocomposites on the inorganic volume fraction. Reproduced from reference [17] with permission from American Chemical Society.