Edited by S. Thomas, Y. Grohens,and P. Jyotishkumar

Characterizationof Polymer Blends

Miscibility, Morphology and Interfaces

Edited by

S. Thomas,

Y. Grohens, and

P. Jyotishkumar

Characterization ofPolymer Blends

Related Titles

Thomas, S., Durand, D., Chassenieux, C., Jyotishkumar, P. (eds.)

Handbook of Biopolymer-Based MaterialsFrom Blends and Composites to Gels and Complex Networks

2013

ISBN: 978-3-527-32884-0 (Also available in electronic formats)

Isayev, A. I. (ed.)

Encyclopedia of Polymer BlendsVolume 1: Fundamentals

2010

ISBN: 978-3-527-31929-9

Isayev, A. I. (ed.)

Encyclopedia of Polymer BlendsVolume 2: Processing

2011

ISBN: 978-3-527-31930-5

Edited by S. Thomas, Y. Grohens, and P. Jyotishkumar

Characterization of Polymer Blends

Miscibility, Morphology and Interfaces

The Editors

Prof. Dr. Sabu ThomasMahatma Gandhi UniversitySchool of Chemical SciencesPriyadarshini Hills P.O.686-560 Kottayam, KeralaIndia

Prof. Dr. Yves GrohensUniversité de Bretagne SudLaboratoire LIMATBRue St Maudé56100 LorientFrance

Prof. Dr. P. JyotishkumarMahatma Gandhi UniversitySchool of Chemical SciencesPriyadarshini Hills P.O.686-560 Kottayam, KeralaIndia

Cover

The transmission electron micrograph inthe background, optical micrograph onthe left, and atomic force micrograph onthe right side of the cover were created byDr. Muruganathan Ramanathan andDr. Seth B. Darling, [Ramanathan, M.and Darling, S.B., Soft Matter, 2009, 5,4665-4671] and are reproduced withkind permission from the authors.

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Contents

List of Contributors XXI

Volume 1

1 Polymer Blends: State of the Art, New Challenges, andOpportunities 1Jyotishkumar Parameswaranpillai, Sabu Thomas, and Yves Grohens

1.1 Introduction 11.2 Miscible and Immiscible Polymer Blends 21.3 Compatibility in Polymer Blends 31.4 Topics Covered in this Book 3

References 5

2 Miscible Blends Based on Biodegradable Polymers 7Emilio Meaurio, Natalia Hernandez-Montero, Ester Zuza,and Jose-Ramon Sarasua

2.1 Introduction 72.2 Thermodynamic Approach to the Miscibility of Polymer Blends 82.2.1 Introduction 82.2.2 Molecular Size and Entropy 82.2.3 The Regular Solution 102.2.4 The Flory–Huggins Model 132.2.5 The Hildebrand Approach 172.2.6 Extension of the Flory–Huggins Model to Systems with Specific

Interactions 192.2.7 The Dependence of Miscibility on Blend Composition and

Temperature 242.2.8 The Painter–Coleman Association Model (PCAM) 252.2.9 Analysis of the Miscibility Using Molecular Modeling

Calculations 262.2.10 Classification of Miscible Systems 272.2.10.1 Entropically Driven Miscible Systems 272.2.10.2 Enthalpically Driven Miscible Systems 28

jV

2.3 Revision of Polymer Blends Based on Biodegradable Polyesters 292.3.1 Blends Containing Poly(lactic acid) or Poly(lactide) (PLA) 292.3.1.1 PLA/PLA Blends 302.3.1.2 PLA Blended with Poly(ethylene glycol) (PEG) and

Poly(ethylene oxide) (PEO) 342.3.1.3 PLA Blended with Poly(vinyl alcohol) (PVA) and

Poly(vinyl acetate) 362.3.1.4 PLA/Poly(e-caprolactone) (PCL) Blends 372.3.1.5 PLA/Poly((R)-3-Hydroxybutyric acid)) (PHB) Blends 402.3.1.6 PLA Blended with Poly(methyl methacrylate) (PMMA)

and Poly(methyl acrylate) (PMA) 412.3.1.7 PLA/Poly(4-vinylphenol) (PVPh) Blends 432.3.1.8 PLA Blended with Poly(butylene succinate) (PBS) and

Poly(ethylene succinate) (PESu) 452.3.1.9 PLA Blended with Poly(propylene carbonate) (PPC) and

Poly(trimethylene carbonate) (PTMC) 472.3.1.10 PLA/Poly(styrene) (PS) Blends 482.3.1.11 PLA Blended with Other Polymers 482.3.1.12 PLA Blended with Other Copolymers 502.3.2 Blends Containing Poly(e-caprolactone) (PCL) 502.3.3 Blends Containing Poly(hydroxy butyrate) (PHB) 502.3.4 Blends Containing Poly(p-dioxanone) (PPDO) 512.3.5 Blends Containing Poly(glycolic acid) (PGA) or Polyglycolide 522.4 Revision of Blends Based on Natural Polymers 522.4.1 Blends Containing Starch 522.4.2 Blends Containing Cellulose 542.4.3 Blends Containing Chitosan 552.4.4 Blends Containing Collagen 56

Appendix 2.A Relevant Research Papers 57Appendix 2.B List of Abbreviations and Nomenclature 832.B.1 Chemical Terms 832.B.2 Polymers and Copolymers 832.B.3 Notations 842.B.4 Symbols 852.B.5 Greek Letters 86Acknowledgments 86References 86

3 Thermodynamics and Morphology and Compatibilizationof Polymer Blends 93Zden9ek Star�y

3.1 Introduction 933.2 Thermodynamics of Polymer Blends 953.2.1 Enthalpy of Mixing 953.2.2 Entropy of Mixing 96

VIj Contents

3.2.3 Flory–Huggins Theory 983.3 Phase Behavior of Polymer Blends 1003.3.1 Phase Diagrams 1013.3.2 Phase Separation 1043.3.3 Interfaces in Polymer Blends 1073.4 Morphology of Polymer Blends 1113.4.1 Morphology Development During Melt Processing 1143.4.2 Stability of Blend Morphology 1193.5 Compatibilization of Polymer Blends 1203.5.1 Morphology Development in Compatibilized Blends 1213.5.2 Compatibilization Techniques 1233.5.2.1 Addition of Preprepared Copolymer 1243.5.2.2 Addition of Reactive Polymer 1253.5.2.3 Addition of Reactive Low-Molecular-Weight Compounds 1253.5.2.4 Other Compatibilization Techniques 126

References 126

4 Characterization of Polymer Blends: Rheological Studies 133Yingfeng Yu

4.1 Introduction 1334.1.1 General Description of Thermoset Rheological Behaviors 1334.1.2 Thermosetting Resins: Gelation, Vitrification, and Viscoelasticity 1344.1.3 Methods of Rheological Measurement 1374.2 Thermosetting Blend Systems with Rubbers and Thermoplastics 1384.2.1 Phase Separation and Rheological Behavior of Rubber-Modified

Systems 1384.2.2 Phase Separation and Rheological Behavior of

Thermoplastic-Modified Systems 1404.2.3 Viscoelastic Properties of the Blends 1434.2.4 Gelation Behaviors of the Blends 1484.3 Thermosetting Systems with Nanostructures 1504.4 Conclusions 153

References 153

5 Characterization of Phase Behavior in Polymer Blends by LightScattering 159Petr Svoboda

5.1 Introduction 1595.2 Amorphous/Crystalline Polymer Blends 1605.3 Light Scattering 1615.4 Cloud-Point Determination 1625.5 Time-Resolved Light Scattering 1655.5.1 Immiscible Blends 1655.5.2 Spinodal Decomposition 1665.5.3 Crystallization byHv Light Scattering 169

Contents jVII

5.5.4 Model Blend of Poly(e-Caprolactone) (PCL) and Poly(Styrene-co-Acrylonitrile) (SAN) 170

5.5.5 Samples Preparation 1715.5.6 Phase Separation and Phase Dissolution in Poly(e-Caprolactone)/

Poly(Styrene-co-Acrylonitrile) Blend 1725.5.7 Crystallization Kinetics by Optical Microscopy and by Hv Light

Scattering 1815.5.8 Competition of Phase Dissolution and Crystallization 1905.6 Determination of Virtual UCST Behavior 1975.6.1 Evaluation of Particle Size in Immiscible Blends 204

Acknowledgments 205References 205

6 Characterization of Polymer Blends by X-Ray Scattering: SAXS andWAXS 209Jitendra Sharma

6.1 Introduction 2096.1.1 Development of SAXS Techniques for Polymers 2126.1.2 Instrumentation and the Synchrotron Advantage 2126.2 Basics of X-Ray Scattering 2136.2.1 Elastic Scattering of Electromagnetic Radiation by

Single Electron 2136.2.2 Scattering by Assembly of Electrons: Scattering Geometry and

Interference 2156.2.3 Scattered Intensity 2166.3 Small- and Wide-Angle X-Ray Scattering (SAXS and

WAXS) 2186.4 Polymer Blend Morphology 2196.4.1 Blends of Homopolymers 2196.4.1.1 Structural Characterization: SAXS Data 2206.4.1.2 Crystallinity: WAXS Data 2246.4.2 Blends of Block Copolymers 2246.4.3 Time-Resolved Studies: Kinetics of Crystallization and

Melting 2286.5 Conclusions 231

References 232

7 Characterization of Polymer Blends and Block Copolymers by NeutronScattering: Miscibility and Nanoscale Morphology 237Kell Mortensen

7.1 Introduction 2377.2 Small-Angle Scattering 2377.2.1 Contrast 2397.2.2 Scattering Function 2427.2.3 Gaussian Chain 244

VIIIj Contents

7.3 Thermodynamics of Polymer Blends and Solutions. Flory–HugginsTheory 246

7.4 The Scattering Function and Thermodynamics 2497.4.1 The Forward Scattering 2507.4.2 Random Phase Approximation (RPA) 2547.4.3 Beyond Mean Field 2587.5 Block Copolymers 2607.5.1 Ordered Phases 264

References 268

8 Ultrasound in Polymer Blends 269Sangmook Lee and Jae Wook Lee

8.1 Introduction 2698.2 High-Frequency Ultrasound 2708.2.1 Static Characterization 2708.2.1.1 Miscibility of Solution Blends 2708.2.1.2 Compatibility 2738.2.1.3 Density 2748.2.1.4 Phase Inversion 2758.2.1.5 Molecular Orientation 2768.2.2 In-Line Monitoring 2788.2.2.1 Morphology 2788.3 Power Ultrasound 2808.3.1 Injection Molding 2808.3.1.1 Weld Line Strength Improvement 2808.3.2 Batch Melt Mixing 2818.3.2.1 Compatibilization 2828.3.3 Extrusion 2838.3.3.1 Molecular Weight Control 2848.3.3.2 Tensile Properties Enhancement 2848.3.3.3 Compatibilization 2868.3.3.4 Rheological Modification 2878.3.3.5 Morphology Control 2898.3.3.6 Die Swell Reduction 2908.4 Summary 292

References 293

9 Characterization of Polymer Blends: Ellipsometry 299�Eva Kiss

9.1 Ellipsometry 2999.1.1 Principles of Ellipsometry 2999.1.2 Thickness and Optical Properties of Layers on Solid Supports 3009.1.2.1 Linear EMA 3019.1.2.2 Maxwell–Garnett EMA 3019.1.2.3 Bruggeman EMA 302

Contents jIX

9.1.3 Depth Profiling 3039.1.4 Sample Preparation 3039.1.5 Types of Instrument and Measurements 3039.1.5.1 Spectroscopic Ellipsometry, Real-Time Measurement 3049.2 Applications in the Characterization of Polymer Blend Films 3049.2.1 Phase Separation in Thin Polymer Blend Films 3049.2.2 Analysis of Interfacial Thickness and Interfacial Reaction 3059.2.2.1 Miscibility 3059.2.2.2 Reactive Compatibilization 3089.2.3 Morphology, Roughness, and Pattern Formation in Nanolayers 3099.2.4 Biomaterial Surfaces 3129.2.5 Surface Modification, Adsorption from Solution 3129.2.5.1 Biomaterial Blends 3139.2.5.2 Distribution and Release of Drugs 3159.2.6 Composite Layers for Organic Solar Cells 3179.3 Concluding Remarks 322

Acknowledgments 322References 323

10 Inverse Gas Chromatography 327Kasylda Milczewska and Adam Voelkel

10.1 Concept and History of Inverse Gas Chromatography (IGC) 32710.2 Theoretical Background 32810.3 Thermodynamic Aspects: Parameters Used for Polymer Blend

Characterization 33010.3.1 Flory–Huggins Interaction Parameter for Polymer–Test Solute

Systems 33110.3.2 Flory–Huggins Interaction Parameter for “Multiple” Systems 33310.4 Procedures Used in IGC Experiments Leading to the Determination

of Polymer Blend Characteristics 33410.5 Application of Chemometric Methods 33610.6 Transport Properties of Polymeric Mixtures 33710.7 Usefulness of IGC: Applications of IGC-Derived Parameters in the

Characterization of Various Systems 34010.8 Advantages and Drawbacks of IGC 341

References 342

11 Thermal Analysis in Polymer Blends 347Ramesh T. Subramaniam and R. Shanti Rajantharan

11.1 Introduction to Polymer Blends 34711.1.1 The Principle of Polymer Blending 34811.2 Experimental 34911.2.1 System 1: PVC/PEO Blends 34911.2.2 System 2: PVC/PEO:LiCF3SO3 Blends 35011.2.3 System 3: PVC/PEO-LiCF3SO3-DBP:EC Blends 351

Xj Contents

11.2.4 System 4: PVC/PEO-LiCF3SO3-DBP-EC:SiO2 Blends 35111.3 Instrumentation 35111.3.1 Sample Weight 35211.3.2 Testing Temperature Range 35211.3.3 Gas Environment 35211.3.4 Heating Rate 35311.4 Thermal Analysis 35311.4.1 Information Obtained from TGA 35311.4.2 Thermal Process 35311.4.3 The Value of the TGA Information 35411.5 Results and Discussion: Thermal Analysis 35511.5.1 Pure PVC 35511.5.2 Pure PEO 35911.5.3 System 1: PVC/PEO Blends 35911.5.4 System 2: PVC/PEO:LiCF3SO3 Blends 36011.5.5 System 3: PVC/PEO-LiCF3SO3-DBP:EC Blends 36111.5.6 System 4: PVC-PEO-LiCF3SO3-DBP-EC:SiO2 Blends 36211.6 Conclusion 362

References 363

12 Dynamic Mechanical Thermal Analysis of Polymer Blends 365Jos�e-David Badia, Laura Santonja-Blasco,Alfonso Martínez-Felipe, and Amparo Ribes-Greus

12.1 Dynamic Mechanical Thermal Analysis (DMTA) 36512.1.1 The DMTA Analyzers 36612.1.2 Using DMTA to Analyze the Viscoelastic Behavior

of Polymers 36812.1.3 Description of DMTA Results: The Viscoelastic Spectra 36912.1.3.1 The Glassy State 36912.1.3.2 The Glass–Rubber Relaxation 37112.1.3.3 Rubbery Plateau 37212.1.3.4 Recrystallization or Curing 37212.1.3.5 Flowing 37312.1.4 Modeling the Viscoelastic Behavior 37312.2 Miscibility Studies 37312.2.1 Binary Systems 37412.2.2 Ternary Systems 37612.2.3 Influence of Type of Processing 37612.2.4 Recovering Plastic Waste by Polymer Blending 37712.2.5 Influence of Nanoparticles 37712.2.6 The Study of the Rubbery Plateau as an Indicator of Miscibility 37812.2.7 Theoretical Approaches to Calculating the Glass–Rubber Relaxation

Temperature 37912.3 Segmental Dynamics, Fragility Index, and Free-Volume 37912.4 Effects of Plasticizers and Chemical and Physical Crosslinks 381

Contents jXI

12.4.1 Influence of Plasticizers on Viscoelastic Performance of PolymerBlends 382

12.4.2 Influence of Chemical and Physical Crosslinkers on the ViscoelasticPerformance of Polymer Blends 383

12.4.3 Strategies to Tune the Heat Distortion Temperature by PolymerBlending 384

12.5 Summary 386References 387

13 Thermomechanical Analysis and Processing of Polymer Blends 393Suchart Siengchin

13.1 Introduction 39313.2 Polymer Toughness 39413.3 Thermomechanical Analysis and Manufacture of Polymer Blends 39513.3.1 Theoretical Background 39613.3.1.1 Dynamic Mechanical Thermal Analysis (DMTA) 39613.3.1.2 Creep Response 39713.3.1.3 Thermogravimetric Analysis 39913.3.2 Latex and Online-Manufacturing Concept of Polymer Blends 39913.3.3 Materials Systems Studied 40213.4 Results and Discussion 40313.4.1 POM/PU Blend 40313.4.2 PA-6/HNBR Blend 40813.5 Summary 41213.5.1 Greek Symbols 413

Acknowledgment 413References 413

14 Water Sorption and Solvent Sorption Behavior 417Fatemeh Sabzi

14.1 Introduction 41714.2 Water Sorption 41814.2.1 Chitosan Blends 41814.2.2 PVP/Polysulfone Blend 42014.2.3 PEOX Blends 42214.2.4 PES/PEO Blend 42214.2.5 Phenoxy Blends 42314.2.6 Poly(ethylene terephthalate) (PET) Nanocomposites 42314.2.7 PMMA/HHIS and PMMA/HS 42414.2.8 PVC/EVAc 42514.2.9 PBI/PI 42814.2.10 PP/EVA 42814.2.11 PVA/P(AA-AMPS) 43014.2.12 PVP/PEG 43114.2.13 iPHB/aPHB and iPHB/PECH 431

XIIj Contents

14.2.14 Epoxy Resin/PEI 43214.2.15 PMMA/PEO 43314.3 Pervaporation 43414.3.1 THF/Water Mixtures 43414.3.2 Acetic Acid/Water Mixture 43514.3.3 Ethanol/Water Mixture 43514.3.4 DMF/Water Mixtures 43614.3.5 1,4-Dioxane/Water 43614.4 Vapor Permeation 43714.4.1 Chitosan/CPA 43714.4.2 Natural Rubber Blends 43714.4.3 NBR Blends 44014.4.4 LCP Blends 44114.4.5 PU/PDMS 44214.4.6 EEA-CB 44214.4.7 PVC/EVAc 44314.4.8 PHB/PEO and PHB/PMMA 44314.4.9 PVA/PAA 44314.5 Gas Permeation 44414.5.1 PVA/PEI/PEG 44414.5.2 PS/PC 44414.5.3 PS/PPO 44514.5.4 PS/PTMPS 44514.5.5 Matrimid/PSF 44614.5.6 Matrimid/P84 44614.5.7 Matrimid/PBI 44714.5.8 CA/PMMA 44714.5.9 PU/PMMA 44814.5.10 EVA-45/H-48 44814.5.11 PS/PVME 44814.5.12 TLCP/PET 44914.5.13 CELL/PVA 44914.5.14 Trogamid Blends 44914.5.15 TPX/Siloxane 45014.5.16 PTMSMMA/3-Methylsulfolane 45014.5.17 BCPC/PMMA 45014.6 Conclusions 451

References 451

15 Modeling and Simulation 457Yingrui Shang and David Kazmer

15.1 Introduction 45715.1.1 Numerical Models for Polymer Blends 45715.1.2 Spinodal Decomposition 46115.1.3 Cahn–Hilliard Equation 464

Contents jXIII

15.1.4 Numerical Method 46515.2 Numerical Simulation of Phase Separation of Immiscible Polymer

Blends on a Heterogeneously Functionalized Substrate 46615.2.1 Fundamentals 46715.2.2 Numerical Method 46815.2.3 Implementation 47015.2.4 Results and Discussion 47115.2.5 Summary 47915.3 Numerical Simulation of the Self-Assembly of a Polymer–Polymer–

Solvent Ternary System on a Heterogeneously FunctionalizedSubstrate 481

15.3.1 Introduction 48115.3.2 Thermodynamics 48115.3.3 Numerical Method 48415.3.4 Implementation 48515.3.5 Results and Discussion 48615.3.6 Summary 49615.4 Verification of Numerical Simulation of the Self-Assembly of a

Polymer–Polymer–Solvent Ternary System on a HeterogeneouslyFunctionalized Substrate 497

15.4.1 Experiment 49815.4.2 Implementation 49915.4.3 Results and Discussion 50115.4.4 Summary 51115.5 Effects of Pattern Shapes and Block Copolymer 51315.6 Conclusions 515

Acknowledgments 517References 517

Volume 2

16 Optical Microscopy (Polarized, Interference, and Phase-ContrastMicroscopy) and Confocal Microscopy 523Muruganathan Ramanathan and Seth B. Darling

16.1 Introduction 52316.2 Optical and Confocal Microscopy: A Brief Overview 52416.3 Mesoscale Morphologies in Polymer Blends: Spherulites and

Microcrystallites 52616.4 Optical Characterization of Mesoscale Morphologies in Polymer

Blends 52816.4.1 Crystalline–Crystalline Blend 52816.4.2 Crystalline–Amorphous Blend 53116.4.3 Role of Polymer Tacticity on Polymer Blend

Morphologies 535

XIVj Contents

16.4.4 Crystallization Morphologies in Stereocomplexationable ChiralBlends 537

16.4.5 Mesoscale Morphologies in ConductingPolymer Blends 540

16.5 Confocal Microscopy Characterization of PolymerBlends 543

16.6 Summary 547Acknowledgments 547References 548

17 Electron Microscopic Analysis of Multicomponent Polymersand Blends 551Rameshwar Adhikari

17.1 Introduction and Overview 55117.2 Sample Preparation Techniques 55217.2.1 Thin-Film Preparation 55217.2.2 Staining of Thin Sections 55317.2.3 Etching of the Surface 55417.2.4 Specimens for Fracture Behavior Analysis 55417.3 Morphological Characterization 55517.3.1 Blends of Semicrystalline Polymers 55517.3.2 Blends of Amorphous Polymers 56117.3.3 Nanostructured Copolymers and Blends 56317.4 Special Techniques and Applications 56717.5 Deformation Studies on Polymer Blends 57117.6 Concluding Notes 574

Acknowledgments 575References 575

18 Characterization of Polymer Blends Using SIMS and NanoSIMS 579Vanna Torrisi

18.1 Introduction 57918.2 Thin Films and Ultrathin Films of Polymer Blends 58018.2.1 Phase-Separation Phenomena 58318.2.2 Technological Applications of Thin and Ultrathin Films of Polymer

Blends 58618.2.3 The Necessity of Compositional Information 58818.3 SIMS: The Techniques and Outputs 58918.3.1 ToF-SIMS: The Technique 59218.3.1.1 Spectra, Profiling, and Imaging Mode 59218.3.1.2 ToF-SIMS: Spatially Resolved Molecular Information 59318.3.1.3 Multivariate Analysis of ToF-SIMS Images 59518.3.2 NanoSIMS: The Technique 59718.3.2.1 NanoSIMS: Ion Optical Set-Up 59718.3.2.2 NanoSIMS: The Mass Spectrometer 597

Contents jXV

18.3.2.3 NanoSIMS: Highly Spatially Resolved ElementalInformation 598

18.4 3D Imaging of Polymer Blends 59918.5 Conclusions and Perspectives 602

References 603

19 Fluorescence Microscopy Techniques for the Structural Analysisof Polymer Materials 609Hiroyuki Aoki

19.1 Introduction 60919.2 Fundamentals of Fluorescence Microscopy 60919.3 Fluorescence Imaging of Polymer Blend Systems 61219.3.1 Real-Space Measurement of 3D Structure 61219.3.2 Spectroscopic Information 61419.4 Fluorescence Microscopy Beyond the Diffraction Barrier 61519.4.1 Near-Field Optical Microscopy 61519.4.2 Super-Resolution Optical Microscopy 61719.4.3 Conformational Analysis of Single Polymer Chain 62019.5 Summary 621

References 622

20 Characterization of Polymer Blends with FTIR Spectroscopy 625Ufana Riaz and Syed Marghoob Ashraf

20.1 Introduction 62520.2 Methods of Investigating Miscibility 62620.2.1 FTIR as a Spectroscopic Tool for the Characterization of Polymer

Blends 62620.2.2 Determination of Miscibility Through Hydrogen

Bonding 62820.3 Characterization of Vinyl Polymer Blends using FTIR

Spectroscopy 62820.3.1 Poly(vinylphenol) (PVPh) Blends 62820.3.2 Poly(vinylpyrrolidone) (PVP) Blends 63220.3.3 Poly(vinyl alcohol) (PVA) Blends 63720.4 Characterization of Blends of Polyethers (PE) using FTIR

Spectroscopy 64320.4.1 Polyethylene Oxide (PEO) Blends 64320.4.2 Poly (vinyl methyl ether) (PVME) Blends 65020.5 Characterization of Acrylate Blends with FTIR

Spectroscopy 65520.5.1 Poly(methylmethacrylate) (PMMA) Blends 65520.5.2 Poly-(3-hydroxybutyrate-co-3-hydroxyvalerate)

(PHBV) Blends 65720.6 Characterization of Synthetic Rubber using

FTIR Spectroscopy 661

XVIj Contents

20.7 Characterization of Natural Polymer Blends Using FTIRSpectroscopy 663

20.7.1 Collagen Blends 66320.7.2 Chitosan Blends 66420.8 Study of Blends by Polarization Modulation and 2D-FTIR

Spectroscopy 66520.9 Analysis of Polymer Blends Using FTIR Microspectroscopy 66820.10 Conclusions 669

Acknowledgments 670Abbreviations 670References 671

21 Characterization of Polymer Blends with Solid-State NMRSpectroscopy 679Mohammad Mahdi Abolhasani and Vahid Karimkhani

21.1 Introduction 67921.2 Miscibility 68021.3 Proton Spin-Lattice Relaxation Experiments 68021.4 Experiments for the Direct Observation of Proton

Spin-Diffusion 68821.5 Molecular Dynamics 69221.5.1 2HNMR Line Shape Analysis 69221.5.2 Polarization Inversion Spin Exchange at the Magic Angle (PISEMA)

Experiment 69421.5.3 Two-Dimensional Wideline Separation (WISE) NMR 69521.6 Organic Solar Cells 69621.7 Conclusions 700

References 702

22 Characterization of Polymer Blends by Infrared, Near-Infrared,and Raman Imaging 705Harumi Sato, Miriam Unger, Dieter Fischer, Yukihiro Ozaki, andHeinz W. Siesler

22.1 Instrumentation for Mid-Infrared and Near-Infrared Imaging 70522.2 Raman Microspectroscopy 70922.3 Characterization of Polymer Blends by FT-IR Imaging 71122.3.1 Investigation of Phase Separation in Biopolymer Blends 71122.3.1.1 Poly((3-Hydroxybutyrate)(PHB)/Poly(L-Lactic Acid)(PLA) Blends 71122.3.1.2 FT-IR Imaging of Anisotropic PHB/PLA Blend Films 71422.3.1.3 Variable-Temperature FT-IR and Raman Imaging Spectroscopy of a

Phase-Separated PHB/PLA 50/50 wt% Blend Film 71722.3.1.4 FT-IR Imaging of the State of Order of PHB/PCL Blend Films 72022.3.1.5 FT-IR and FT-NIR Imaging of the Spherulitic Structure of

Poly(3-Hydroxy-Butyrate) and Cellulose AcetateButyrate Blends 724

Contents jXVII

22.3.1.6 Raman Mapping Measurements of the Influence of aCompatibilizer on Phase Separation of the Polymer BlendPolypropylene/Polyamide 6 728References 730

23 Electron Paramagnetic Resonance Spectroscopy and Forward RecoilSpectrometry 731Krzysztof Kruczała and Ewa Szajdzi�nska-Pietek

23.1 Introduction 73123.2 Electron Paramagnetic Spectroscopy 73223.2.1 EPR Background 73223.2.1.1 Multifrequency EPR 73623.2.1.2 Pulsed EPR 73723.2.1.3 EPR Imaging 73823.2.1.4 Simulation of EPR Spectra 74123.2.1.5 Spin Probes and Spin Labels 74423.2.2 EPR Applications in Studies of Polymer Blends 74723.2.2.1 Spin Probing of the Structure and Dynamics 74723.2.2.2 Radical Processes Induced by Ionizing Radiation 75523.2.2.3 Conductive Materials 76123.3 Forward Recoil Spectrometry 76623.3.1 FRES Fundamentals 76723.3.2 Technique Developments 76923.3.2.1 Time-of-Flight FRES 77023.3.2.2 Low-Energy FRES 77123.3.2.3 Heavy Ion FRES 77223.3.3 Applications to Polymer Blend Studies 77323.3.3.1 Tracer Diffusion 77323.3.3.2 Reaction Kinetics 77523.3.3.3 Surface and Interfaces 77623.3.3.4 Phase Separation 778

Acknowledgments 782References 783

24 Characterization of Polymer Blends Using UV-VisibleSpectroscopy 789Mamdouh H. Abou-Taleb

24.1 Introduction 78924.2 Electromagnetic Radiation 79124.3 Interaction of Radiation (UV/VIS) with Matter 79224.4 The Nature of Electronic Excitations in Matter

(Polymer Blends) 79324.5 Relationship of Structure of Matter to the Electronic Absorption

Spectrum 79624.6 The Correspondence of Color and Transparent Spectrum 796

XVIIIj Contents

24.7 Relationship of Polymer Blends to Material Characterization 79824.8 Optical Properties of Semiconductors (Polymers and Polymer

Blends) 80124.9 Optical Absorption Spectra of Materials 80224.9.1 Extended-to-Extended State Transitions 80324.9.2 Extended-to-Localized and Localized-to-Extended State

Transitions 80324.9.3 Localized-to-Localized State Transitions 80424.9.4 Exciton Absorption 80724.9.5 Free Carrier Absorption 80724.10 Instrumentation 80924.10.1 Single-Beam Spectrophotometry 80924.10.2 Double-Beam Spectrophotometry 81024.11 Radiation Sources 81124.11.1 Xenon Lamp (Xenon Arc Lamp) 81124.11.2 Deuterium Lamp 81124.12 Monochromator 81124.12.1 Wavelength Selection 81224.13 Detection Area and Detectors 81224.13.1 Photomultiplier 81224.13.2 Silicon Photodiode 81324.13.3 Photodiode Array 81324.14 Data Acquisition 81424.15 Classification of Errors in Spectrophotometry 81424.15.1 Spectral Band Width and Slit Width 81524.15.2 Slit Height 81624.15.3 Stray Light 81624.15.4 Solvents 817

References 817

25 Fluorescence Spectroscopy 821Gabriel Bernardo and Jorge Morgado

25.1 Introduction 82125.2 Fundamentals of Fluorescence Spectroscopy 82225.2.1 Theory 82225.2.2 Steady-State Fluorescence 82325.2.3 Time-Resolved Fluorescence 82325.2.4 Fluorescence Quenching 82725.2.5 Fluorescence Microscopy 83025.3 Intrinsically Fluorescent Polymer Blends 83025.4 Systems Requiring Extrinsic Fluorescent Labels 84025.5 Conclusions 844

Nomenclature 844Acknowledgments 845References 846

Contents jXIX

26 Characterization of Polymer Blends by Dielectric Spectroscopyand Thermally Simulated Depolarization Current 849Samy A. Madbouly and Michael R. Kessler

26.1 Introduction 84926.1.1 Dielectric Relaxation Spectroscopy and Thermally Stimulated

Depolarization Current 84926.1.2 Analysis of Relaxation Spectrum 85026.1.3 Effect of Temperature on Relaxation Spectrum 85226.2 Dielectric Relaxation Spectroscopy of Amorphous Polymer

Blends 85326.3 Dielectric Relaxation Spectroscopy of Semicrystalline Polymer

Blends 86226.4 Dielectric Relaxation Spectroscopy of Chemically Reactive Polymer

Blends 86826.5 Conclusions 872

References 873

27 Positron Annihilation Spectroscopy: Polymer Blends and Miscibility 877Chikkakuntappa Ranganathaiah

27.1 Introduction 87727.2 Positron Annihilation Spectroscopy 87827.2.1 The Positron Annihilation Process 87827.2.2 Positronium 88027.2.2.1 Positron and Positronium Sensitivity to Defects and Free

Volume 88227.2.2.2 Models Predicting Positronium Formation 88327.3 Free Volume Theory 88427.3.1 Free Volume Model and Positronium Lifetime Connection 88527.4 Characterization of Polymer Blends by PAS 88727.5 Experimental Methods of PAS 88827.5.1 Positron Annihilation Lifetime Spectroscopy (PALS) 88827.5.1.1 Free Volume Distribution-Lifetime Analysis by Laplace Transform

Method 89127.5.1.2 Free-Volume Distributions in Polymer Blends 89227.5.1.3 Angular Correlation of Annihilation Radiation (ACAR) Method 89327.5.1.4 Doppler Broadening of the Annihilation Radiation (DBAR)

Method 89427.6 Miscibility in Polymer Blends and Free Volume 89627.6.1 Free Volume and Miscibility Studies in Blends 90127.7 Future Outlook 916

Acknowledgments 916References 916

Index 921

XXj Contents

List of Contributors

Mohammad Mahdi AbolhasaniUniversity of KashanChemical Engineering DepartmentKashanIran

Mamdouh H. Abou-TalebCairo UniversityFaculty of SciencePhysics DepartmentGizaEgypt

and

Taif UniversityFaculty of SciencePhysics Department21974 TaifSaudi Arabia

Rameshwar AdhikariTribhuvan UniversityCentral Department of ChemistryKirtipurKathmanduNepal

and

Nepal Polymer Institute (NPI)KathmanduNepal

Hiroyuki AokiKyoto UniversityAdvanced Biomedical EngineeringResearch UnitKyoto-Daigaku-KatsuraNishikyoKyoto 615–8510Japan

Syed Marghoob AshrafJamia Millia Islamia (A CentralUniversity)Department of ChemistryMaterials Research LaboratoryMaulana Mohammad Ali JauharMargNew Delhi 110025India

Jos�e-David BadiaUniversitat Polit�ecnica de Val�enciaInstituto de Tecnología de MaterialesCamino de Vera, s/n46022 Val�enciaSpain

jXXI

Gabriel BernardoUniversity of MinhoInstitute for Polymers andComposites/I3NCampus de Azur�em4800-058 Guimar~aesPortugal

Seth B. DarlingArgonne National LaboratoryCenter for Nanoscale Materials9700 South Cass AvenueArgonne, IL60439USA

and

University of ChicagoInstitute for Molecular Engineering5801 South Ellis AvenueChicago, IL 60637USA

Dieter FischerLeibniz-Institute forPolymer ResearchHohe Str. 601069 DresdenGermany

Yves GrohensUniversit�e de Bretagne SudLaboratoire Ing�enierie des Mat�eriauxde BretagneRue St Maud�e56100 LorientFrance

Natalia Hernandez-MonteroUniversity of the Basque Country(UPV/EHU)School of EngineeringDepartment of Mining-MetallurgyEngineering & Materials SciencePOLYMAT – Basque Center forMacromolecular Design andEngineeringAlameda de Urquijo s/n.48013 BilbaoSpain

Vahid KarimkhaniAmirkabir University of TechnologyDepartment of Polymer Engineeringand Color TechnologyTehranIran

and

Case Western Reserve UniversityDepartment of MacromolecularScience and Engineering2100 Adelbert RoadCleveland, OH 44106USA

David KazmerUniversity of Massachusetts at LowellDepartment of Plastics Engineering1 University AvenueLowell, MA 01854USA

Michael R. KesslerWashington State UniversitySchool of Mechanical and MaterialsEngineeringPullman, WA 99164USA

XXIIj List of Contributors

�Eva KissE€otv€os Lor�and UniversityInstitute of ChemistryLaboratory of Interfaces andNanostructuresP�azm�any P. s. 1/a1117 BudapestHungary

Krzysztof KruczałaJagiellonian UniversityFaculty of ChemistryUl. Ingardenia 3/13930-060 KrakowPoland

Jae Wook LeeSogang UniversityDepartment of Chemical andBiomolecular EngineeringApplied Rheology CenterSeoul 121–742Korea

Sangmook LeeDankook UniversityDivision of Chemical Engineering126, Jukjeon-dong, Suji-guGyeonggi-do 448–701Korea

Samy A. MadboulyIowa State UniversityDepartment of Materials Science andEngineeringAmes, IA 50011USA

and

Cairo UniversityFaculty of ScienceDepartment of ChemistryOrman-Giza 12613Egypt

Alfonso Martínez-FelipeUniversitat Polit�ecnica de Val�enciaInstituto de Tecnología de MaterialesCamino de Vera, s/n46022 Val�enciaSpain

Emilio MeaurioUniversity of the Basque Country(UPV/EHU)School of EngineeringDepartment of Mining-MetallurgyEngineering & Materials SciencePOLYMAT – Basque Center forMacromolecular Design andEngineeringAlameda de Urquijo s/n.48013 BilbaoSpain

Kasylda MilczewskaPoznan University of TechnologyInstitute of Chemical Technology andEngineeringpl. M. Sk»odowskiej-Curie 260-965 PoznanPoland

Jorge MorgadoInstituto de TelecomunicaSc~oesAv. Rovisco Pais1049-001 LisbonPortugal

and

Instituto Superior T�ecnicoDepartment of BioengineeringUL, Av. Rovisco Pais1049-001 LisbonPortugal

List of Contributors jXXIII

Kell MortensenUniversity of CopenhagenNiels Bohr InstituteUniversitetsparken 5, D3062100 CopenhagenDenmark

Yukihiro OzakiKwansei Gakuin UniversitySchool of Science and TechnologySandaHyogo 669–1337Japan

Jyotishkumar ParameswaranpillaiCochin University of Science andTechnologyDepartment of Polymer Science andRubber TechnologyCochinKerala 682022India

R. Shanti RajantharanUniversity of MalayaFaculty of ScienceDepartment of PhysicsCentre for Ionics University ofMalayaJalan Lembah Pantai50603 Kuala LumpurMalaysia

Muruganathan RamanathanOak Ridge National LaboratoryCenter for Nanophase MaterialsSciencesOne Bethel Valley RdOak Ridge, TN 37831USA

Chikkakuntappa RanganathaiahUniversity of MysoreDepartment of Studies in PhysicsManasagangotriMysore 570006India

and

University of Western AustraliaSchool of PhysicsARC Center of Excellence – Centerfor Antimatter-Matter Studies35 Stirling Highway CrawleyPerth WA 6009Australia

Ufana RiazJamia Millia Islamia (A CentralUniversity)Department of ChemistryMaterials Research LaboratoryMaulana Mohammad Ali JauharMargNew Delhi 110025India

Amparo Ribes-GreusUniversitat Polit�ecnica de Val�enciaInstituto de Tecnología de MaterialesCamino de Vera, s/n46022 Val�enciaSpain

Fatemeh SabziShiraz University of TechnologyDepartment of ChemicalEngineeringModarres Blv.Shiraz 71555-313Iran

XXIVj List of Contributors

Laura Santonja-BlascoUniversitat Polit�ecnica de Val�enciaInstituto de Tecnología de MaterialesCamino de Vera, s/n46022 Val�enciaSpain

Jose-Ramon SarasuaUniversity of the Basque Country(UPV/EHU)School of EngineeringDepartment of Mining-MetallurgyEngineering & Materials SciencePOLYMAT – Basque Center forMacromolecular Design andEngineeringAlameda de Urquijo s/n.48013 BilbaoSpain

Harumi SatoKobe UniversityGraduate School of HumanDevelopment and EnvironmentNada-kuKobeHyogo 657–8501Japan

Yingrui ShangTianjin UniversityCollege of Material Science andEngineeringDepartment of Polymer Science andEngineeringTianjinChina

Jitendra SharmaShri Mata Vaishno Devi UniversitySchool of PhysicsKakriyal KatraReasiJammu & Kashmir 182320India

Suchart SiengchinKing Mongkut’s University ofTechnology North BangkokThe Sirindhorn InternationalThai-German Graduate School ofEngineering (TGGS)Department of Mechanical andProcess Engineering1518 Wongsawang RoadBangsueBangkok 10800Thailand

Heinz W. SieslerUniversity of Duisburg-EssenDepartment of Physical ChemistrySchuetzenbahn 7045117 EssenGermany

Zden9ek Star�yFriedrich-Alexander-UniversityErlangen-NurembergInstitute of Polymer MaterialsMartensstrasse 791058 ErlangenGermany

Ramesh T. SubramaniamUniversity of MalayaFaculty of ScienceDepartment of PhysicsCentre for Ionics University ofMalayaJalan Lembah Pantai50603 Kuala LumpurMalaysia

List of Contributors jXXV

Petr SvobodaTomas Bata University in ZlinFaculty of TechnologyDepartment of Polymer EngineeringNam. T. G. Masaryka 275762 72 ZlinCzech Republic

and

Tomas Bata University in ZlinUniversity InstituteCentre of Polymer SystemsNad Ovcirnou 3685760 01 ZlinCzech Republic

Ewa Szajdzi�nska-PietekJagiellonian UniversityFaculty of ChemistryUl. Ingardenia 3/13930-060 KrakowPoland

Sabu ThomasMahatma Gandhi UniversityInternational and InteruniversityCentre for Nanoscience &NanotechnologyPriyadarshini HillsKottayamKerala 686560India

Vanna TorrisiUniversity of Catania and CSGIDepartment of Chemical SciencesLaboratory for Molecular Surfacesand Nanotechnology (LAMSUN)Viale A. Doria 695125 CataniaItaly

Miriam UngerCETICS Healthcare TechnologiesGmbHSchelztorstraße 54–56Esslingen am NeckarGermany

Adam VoelkelPoznan University of TechnologyInstitute of Chemical Technology andEngineeringpl. M. Sk»odowskiej-Curie 260-965 PoznanPoland

Yingfeng YuFudan UniversityDepartment of MacromolecularScienceState Key Laboratory of MolecularEngineering of PolymersShanghai 200433China

Ester ZuzaUniversity of the Basque Country(UPV/EHU)School of EngineeringDepartment of Mining-MetallurgyEngineering & Materials SciencePOLYMAT – Basque Center forMacromolecular Design andEngineeringAlameda de Urquijo s/n.48013 BilbaoSpain

XXVIj List of Contributors

1Polymer Blends: State of the Art, New Challenges,and OpportunitiesJyotishkumar Parameswaranpillai, Sabu Thomas, and Yves Grohens

1.1Introduction

A polymer blend is a mixture of two or more polymers that have been blendedtogether to create a new material with different physical properties. Generally,there are five main types of polymer blend: thermoplastic–thermoplastic blends;thermoplastic–rubber blends; thermoplastic–thermosetting blends; rubber–thermosetting blends; and polymer–filler blends, all of which have been exten-sively studied. Polymer blending has attracted much attention as an easy andcost-effective method of developing polymeric materials that have versatility forcommercial applications. In other words, the properties of the blends can bemanipulated according to their end use by correct selection of the componentpolymers [1]. Today, the market pressure is so high that producers of plastics needto provide better and more economic materials with superior combinationsof properties as a replacement for the traditional metals and polymers. Although,plastic raw materials are more costly than metals in terms of weight, they are moreeconomical in terms of the product cost. Moreover, polymers are corrosion-resist-ant, possess a light weight with good toughness (which is important for good fueleconomy in automobiles and aerospace applications), and are used for creating awide range of goods that include household plastic products, automotive interiorand exterior components, biomedical devices, and aerospace applications [2].The development and commercialization of new polymer usually requires many

years and is also extremely costly. However, by employing a polymer blending pro-cess – which is also very cheap to operate – it is often possible to reduce the timeto commercialization to perhaps two to three years [2]. As part of the replacementof traditional polymers, the production of polymer blends represents half of allplastics produced in 2010. Today, the polymer industry is becoming increasinglysophisticated, with ultra-high-performance injection molding machines andextruders available that allow phase-separations and viscosity changes to be effec-tively detected or manipulated during the processing stages [3]. Whilst this mod-ern blending technology can also greatly extend the performance capabilities of

1

Characterization of Polymer Blends: Miscibility, Morphology, and Interfaces, First Edition.Edited by S. Thomas, Y. Grohens, and P. Jyotishkumar.� 2015 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2015 by Wiley-VCH Verlag GmbH & Co. KGaA.

polymer blends, increasing market pressure now determines that, for specificapplications, polymer blends must perform under some specific conditions (e.g.,mechanical, chemical, thermal, electrical). This presents a major challenge as thematerials must often function at the limit of the properties that can be achieved;consequently, in-depth studies of the properties and performance of polymerblends are essential.

1.2Miscible and Immiscible Polymer Blends

Generally, polymer blends are classified into either homogeneous (miscible on amolecular level) or heterogeneous (immiscible) blends. For example, poly(styrene)(PS)–poly(phenylene oxide) (PPO) and poly(styrene-acrylonitrile) (SAN)–poly(methyl methacrylate) (PMMA) are miscible blends, while poly(propylene) (PP)–PS and poly(propylene)–poly(ethylene) (PE) are immiscible blends. Miscible (single-phase) blends are usually optically transparent and are homogeneous to the polymersegmental level. Single-phase blends also undergo phase separation that is usuallybrought about by variations in temperature, pressure, or in the composition of themixture.Since, ultimately, the properties of a polymer blend will depend on the final mor-

phology, various research groups have recently undertaken extensive studies of themiscibility and phase behavior of polymer blends. In practice, the physical propert-ies of interest are found either by miscible pairs or by a heterogeneous system,depending on the type of application. Generally, polymer blends can be completelymiscible, partially miscible or immiscible, depending on the value of DGm [4].The free energy of mixing is given by

DGm ¼ DHm � TDSm ð1:1ÞFor miscibility (binary blend), the following two conditions must be satisfied:

the first condition DGm< 0; and the second condition

@2ðDGmÞ@w2

i

� �T ;p

> 0 ð1:2Þ

where DGm is the Gibbs energy of mixing, w is the composition, where w is usu-ally taken as the volume fraction of one of the components.DSm is the entropy factor and is a measure of disorder or randomness, is always

positive and, therefore, is favorable for mixing or miscibility especially for low-molecular-weight solutions. In contrast, polymer solutions have monomers with ahigh molecular weight and hence the enthalpy of mixing (DHm) is also a decidingfactor for miscibility. DHm is the heat that is either consumed (endothermic) orgenerated (exothermic) during mixing. If the mixing is exothermic then thesystem is driven towards miscibility. The mixing is exothermic only whenstrong specific interactions occur between the blend components. The mostcommon specific interactions found in polymer blends are hydrogen bonding,

2 1 Polymer Blends: State of the Art, New Challenges, and Opportunities