Characterization of Polymer Blends: Miscibility, Morphology and Interfaces

Filling the gap for a reference dedicated to the characterization of polymer blends and
their micro and nano morphologies, this book provides comprehensive, systematic
coverage in a one–stop, two–volume resource for all those working in the field.

Leading researchers from industry and academia, as well as from government
and private research institutions around the world summarize recent technical
advances in chapters devoted to their individual contributions. In so doing, they
examine a wide range of modern characterization techniques, from microscopy and
spectroscopy to diffraction, thermal analysis, rheology, mechanical measurements
and chromatography. These methods are compared with each other to assist in
determining the best solution for both fundamental and applied problems, paying
attention to the characterization of nanoscale miscibility and interfaces, both in
blends involving copolymers and in immiscible blends. The thermodynamics,
miscibility, phase separation, morphology and interfaces in polymer blends are also
discussed in light of new insights involving the nanoscopic scale. Finally, the authors
detail the processing–morphology–property relationships of polymer blends, as well
as the influence of processing on the generation of micro and nano morphologies,
and the dependence of these morphologies on the properties of blends. Hot topics
such as compatibilization through nanoparticles, miscibility of new biopolymers and
nanoscale investigations of interfaces in blends are also addressed.

With its application–oriented approach, handpicked selection of topics and expert
contributors, this is an outstanding survey for anyone involved in the field of polymer
blends for advanced technologies.

List of Contributors XXI

Volume 1

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

1.1 Introduction 1

1.2 Miscible and Immiscible Polymer Blends 2

1.3 Compatibility in Polymer Blends 3

1.4 Topics Covered in this Book 3

References 5

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

2.1 Introduction 7

2.2 Thermodynamic Approach to the Miscibility of Polymer Blends 8

2.3 Revision of Polymer Blends Based on Biodegradable Polyesters 29

2.4 Revision of Blends Based on Natural Polymers 52

Appendix 2.A Relevant Research Papers 57

Appendix 2.B List of Abbreviations and Nomenclature 83

2.B.1 Chemical Terms 83

2.B.2 Polymers and Copolymers 83

2.B.3 Notations 84

2.B.4 Symbols 85

2.B.5 Greek Letters 86

Acknowledgments 86

References 86

3 Thermodynamics and Morphology and Compatibilization of Polymer Blends 93
Zdenék Starý

3.1 Introduction 93

3.2 Thermodynamics of Polymer Blends 95

3.3 Phase Behavior of Polymer Blends 100

3.4 Morphology of Polymer Blends 111

3.5 Compatibilization of Polymer Blends 120

References 126

4 Characterization of Polymer Blends: Rheological Studies 133
Yingfeng Yu

4.1 Introduction 133

4.2 Thermosetting Blend Systems with Rubbers and Thermoplastics 138

4.3 Thermosetting Systems with Nanostructures 150

4.4 Conclusions 153

References 153

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

5.1 Introduction 159

5.2 Amorphous/Crystalline Polymer Blends 160

5.3 Light Scattering 161

5.4 Cloud–Point Determination 162

5.5 Time–Resolved Light Scattering 165

5.6 Determination of Virtual UCST Behavior 197

5.6.1 Evaluation of Particle Size in Immiscible Blends 204

Acknowledgments 205

References 205

6 Characterization of Polymer Blends by X–Ray Scattering: SAXS and WAXS 209
Jitendra Sharma

6.1 Introduction 209

6.2 Basics of X–Ray Scattering 213

6.3 Small– and Wide–Angle X–Ray Scattering (SAXS and WAXS) 218

6.4 Polymer Blend Morphology 219

6.5 Conclusions 231

References 232

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

7.1 Introduction 237

7.2 Small–Angle Scattering 237

7.3 Thermodynamics of Polymer Blends and Solutions. Flory Huggins Theory 246

7.4 The Scattering Function and Thermodynamics 249

7.5 Block Copolymers 260

References 268

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

8.1 Introduction 269

8.2 High–Frequency Ultrasound 270

8.3 Power Ultrasound 280

8.4 Summary 292

References 293

9 Characterization of Polymer Blends: Ellipsometry 299
Éva Kiss

9.1 Ellipsometry 299

9.2 Applications in the Characterization of Polymer Blend Films 304

9.3 Concluding Remarks 322

Acknowledgments 322

References 323

10 Inverse Gas Chromatography 327
Kasylda Milczewska and Adam Voelkel

10.1 Concept and History of Inverse Gas Chromatography (IGC) 327

10.2 Theoretical Background 328

10.3 Thermodynamic Aspects: Parameters Used for Polymer Blend Characterization 330

10.4 Procedures Used in IGC Experiments Leading to the Determination of Polymer Blend Characteristics 334

10.5 Application of Chemometric Methods 336

10.6 Transport Properties of Polymeric Mixtures 337

10.7 Usefulness of IGC: Applications of IGC–Derived Parameters in the Characterization of Various Systems 340

10.8 Advantages and Drawbacks of IGC 341

References 342

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

11.1 Introduction to Polymer Blends 347

11.2 Experimental 349

11.3 Instrumentation 351

11.4 Thermal Analysis 353

11.5 Results and Discussion: Thermal Analysis 355

11.6 Conclusion 362

References 363

12 Dynamic Mechanical Thermal Analysis of Polymer Blends 365
José–David Badia, Laura Santonja–Blasco, Alfonso Martínez–Felipe, and Amparo Ribes–Greus

12.1 Dynamic Mechanical Thermal Analysis (DMTA) 365

12.2 Miscibility Studies 373

12.3 Segmental Dynamics, Fragility Index, and Free–Volume 379

12.4 Effects of Plasticizers and Chemical and Physical Crosslinks 381

12.5 Summary 386

References 387

13 Thermomechanical Analysis and Processing of Polymer Blends 393
Suchart Siengchin

13.1 Introduction 393

13.2 Polymer Toughness 394

13.3 Thermomechanical Analysis and Manufacture of Polymer Blends 395

13.4 Results and Discussion 403

13.5 Summary 412

Acknowledgment 413

References 413

14 Water Sorption and Solvent Sorption Behavior 417
Fatemeh Sabzi

14.1 Introduction 417

14.2 Water Sorption 418

14.3 Pervaporation 434

14.4 Vapor Permeation 437

14.5 Gas Permeation 444

14.6 Conclusions 451

References 451

15 Modeling and Simulation 457
Yingrui Shang and David Kazmer

15.1 Introduction 457

15.2 Numerical Simulation of Phase Separation of Immiscible Polymer Blends on a Heterogeneously Functionalized Substrate 466

15.3 Numerical Simulation of the Self–Assembly of a Polymer Polymer Solvent Ternary System on a Heterogeneously Functionalized Substrate 481

15.4 Verification of Numerical Simulation of the Self–Assembly of a Polymer Polymer Solvent Ternary System on a Heterogeneously Functionalized Substrate 497

15.5 Effects of Pattern Shapes and Block Copolymer 513

15.6 Conclusions 515

Acknowledgments 517

References 517

Volume 2

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

16.1 Introduction 523

16.2 Optical and Confocal Microscopy: A Brief Overview 524

16.3 Mesoscale Morphologies in Polymer Blends: Spherulites and Microcrystallites 526

16.4 Optical Characterization of Mesoscale Morphologies in Polymer Blends 528

16.5 Confocal Microscopy Characterization of Polymer Blends 543

16.6 Summary 547

Acknowledgments 547

References 548

17 Electron Microscopic Analysis of Multicomponent Polymers and Blends 551
Rameshwar Adhikari

17.1 Introduction and Overview 551

17.2 Sample Preparation Techniques 552

17.3 Morphological Characterization 555

17.4 Special Techniques and Applications 567

17.5 Deformation Studies on Polymer Blends 571

17.6 Concluding Notes 574

Acknowledgments 575

References 575

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

18.1 Introduction 579

18.2 Thin Films and Ultrathin Films of Polymer Blends 580

18.3 SIMS: The Techniques and Outputs 589

18.4 3D Imaging of Polymer Blends 599

18.5 Conclusions and Perspectives 602

References 603

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

19.1 Introduction 609

19.2 Fundamentals of Fluorescence Microscopy 609

19.3 Fluorescence Imaging of Polymer Blend Systems 612

19.4 Fluorescence Microscopy Beyond the Diffraction Barrier 615

19.5 Summary 621

References 622

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

20.1 Introduction 625

20.2 Methods of Investigating Miscibility 626

20.3 Characterization of Vinyl Polymer Blends using FTIR Spectroscopy 628

20.4 Characterization of Blends of Polyethers (PE) using FTIR Spectroscopy 643

20.5 Characterization of Acrylate Blends with FTIR Spectroscopy 655

20.6 Characterization of Synthetic Rubber using FTIR Spectroscopy 661

20.7 Characterization of Natural Polymer Blends Using FTIR Spectroscopy 663

20.8 Study of Blends by Polarization Modulation and 2D–FTIR Spectroscopy 665

20.9 Analysis of Polymer Blends Using FTIR Microspectroscopy 668

20.10 Conclusions 669

Acknowledgments 670

Abbreviations 670

References 671

21 Characterization of Polymer Blends with Solid–State NMR Spectroscopy 679
Mohammad Mahdi Abolhasani and Vahid Karimkhani

21.1 Introduction 679

21.2 Miscibility 680

21.3 Proton Spin–Lattice Relaxation Experiments 680

21.4 Experiments for the Direct Observation of Proton Spin–Diffusion 688

21.5 Molecular Dynamics 692

21.6 Organic Solar Cells 696

21.7 Conclusions 700

References 702

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

22.1 Instrumentation for Mid–Infrared and Near–Infrared Imaging 705

22.2 Raman Microspectroscopy 709

22.3 Characterization of Polymer Blends by FT–IR Imaging 711

References 730

23 Electron Paramagnetic Resonance Spectroscopy and Forward Recoil Spectrometry 731
Krzysztof Krucza³a and Ewa Szajdzinska–Pietek

23.1 Introduction 731

23.2 Electron Paramagnetic Spectroscopy 732

23.3 Forward Recoil Spectrometry 766

Acknowledgments 782

References 783

24 Characterization of Polymer Blends Using UV–Visible Spectroscopy 789
Mamdouh H. Abou–Taleb

24.1 Introduction 789

24.2 Electromagnetic Radiation 791

24.3 Interaction of Radiation (UV/VIS) with Matter 792

24.4 The Nature of Electronic Excitations in Matter (Polymer Blends) 793

24.5 Relationship of Structure of Matter to the Electronic Absorption Spectrum 796

24.6 The Correspondence of Color and Transparent Spectrum 796

24.7 Relationship of Polymer Blends to Material Characterization 798

24.8 Optical Properties of Semiconductors (Polymers and Polymer Blends) 801

24.9 Optical Absorption Spectra of Materials 802

24.10 Instrumentation 809

24.11 Radiation Sources 811

24.12 Monochromator 811

24.13 Detection Area and Detectors 812

24.14 Data Acquisition 814

24.15 Classification of Errors in Spectrophotometry 814

References 817

25 Fluorescence Spectroscopy 821
Gabriel Bernardo and Jorge Morgado

25.1 Introduction 821

25.2 Fundamentals of Fluorescence Spectroscopy 822

25.3 Intrinsically Fluorescent Polymer Blends 830

25.4 Systems Requiring Extrinsic Fluorescent Labels 840

25.5 Conclusions 844

Nomenclature 844

Acknowledgments 845

References 846

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

26.1 Introduction 849

26.2 Dielectric Relaxation Spectroscopy of Amorphous Polymer Blends 853

26.3 Dielectric Relaxation Spectroscopy of Semicrystalline Polymer Blends 862

26.4 Dielectric Relaxation Spectroscopy of Chemically Reactive Polymer Blends 868

26.5 Conclusions 872

References 873

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

27.1 Introduction 877

27.2 Positron Annihilation Spectroscopy 878

27.3 Free Volume Theory 884

27.4 Characterization of Polymer Blends by PAS 887

27.5 Experimental Methods of PAS 888

27.6 Miscibility in Polymer Blends and Free Volume 896

27.7 Future Outlook 916

Acknowledgments 916

References 916

Index 921

Sabu Thomas is a Professor of Polymer Science and Engineering at Mahatma Gandhi University (India). He is a Fellow of the Royal Society of Chemistry and a Fellow of the New York Academy of Sciences. Thomas has published over 350 papers in peer reviewed journals on polymer composites, membrane separation, polymer blends and alloys, and polymer recycling, has an h–index of 33 and has edited six books.
Yves Grohens is head of the Laboratory for Engineering of Materials (LIMATB) located at the University of South Brittany, France. His research interests include interface science in nano and bio–composites as well as confinement applications and (bio)polymer behaviour in model thin films. Grohens has published more than 120 papers in international journals devoted to polymers and surface science.
P. Jyotishkumar is a Senior Research Fellow pursuing a PhD under the supervision of Sabu Thomas in the School of Chemical Sciences, Mahatma Gandi University, India