Polymer Morphology

Qipeng Guo, DSc, DEng, is the chair professor in polymer science and technology at Deakin University, Australia, where he was awarded a Personal Chair in recognition of his distinguished achievements and international reputation in polymer research,  involving both the fundamental principles in polymer science and the development of new polymer materials. He is a Fellow of The Royal Society of Chemistry.

PREFACE xiii

LIST OF CONTRIBUTORS xv

PART I PRINCIPLES AND METHODS OF CHARACTERIZATION 1

1 Overview and Prospects of Polymer Morphology 3
Jerold M. Schultz

1.1 Introductory Remarks 3

1.2 Experimental Avenues of Morphological Research 4

1.2.1 Morphological Characterization: The Enabling of in situ Measurements 4

1.2.2 Morphology–Property Investigation 5

1.2.3 Morphology Development 7

1.3 Modeling and Simulation 8

1.3.1 Self-Generated Fields 9

1.4 Wishful Thinking 11

1.5 Summary 11

References 12

2 X-ray Diffraction from Polymers 14
N. Sanjeeva Murthy

2.1 Introduction 14

2.2 Basic Principles 14

2.3 Instrumentation 16

2.4 Structure Determination 17

2.4.1 Lattice Dimensions 17

2.4.2 Molecular Modeling 18

2.4.3 Rietveld Method 18

2.4.4 Pair Distribution Functions 18

2.5 Phase Analysis 19

2.5.1 Crystallinity Determination 20

2.5.2 Composition Analysis 21

2.6 Crystallite Size and Disorder 21

2.7 Orientation Analysis 22

2.7.1 Crystalline Orientation 22

2.7.2 Uniaxial Orientation 22

2.7.3 Biaxial Orientation 24

2.7.4 Amorphous Orientation 25

2.8 Small-Angle Scattering 25

2.8.1 Central Diffuse Scattering 26

2.8.2 Discrete Reflections from Lamellar Structures 27

2.8.3 Small-Angle Neutron Scattering and Solvent Diffusion 29

2.9 Specialized Measurements 30

2.9.1 In situ Experiments 30

2.9.2 Microbeam Diffraction 31

2.9.3 Grazing Incidence Diffraction 32

2.10 Summary 33

References 33

3 Electron Microscopy of Polymers 37
Goerg H. Michler and Werner Lebek

3.1 Introduction 37

3.2 Microscopic Techniques 37

3.2.1 Scanning Electron Microscopy (SEM) 37

3.2.2 Transmission Electron Microscopy (TEM) 42

3.2.3 Comparison of Different Microscopic Techniques 45

3.2.4 Image Processing and Image Analysis 46

3.3 Sample Preparation 47

3.4 In situ Microscopy 50

References 52

4 Characterization of Polymer Morphology by Scattering Techniques 54
Jean-Michel Guenet

4.1 Introduction 54

4.2 A Short Theoretical Presentation 55

4.2.1 General Expressions 55

4.2.2 The Form Factor 56

4.3 Experimental Aspects 60

4.3.1 The Contrast Factor 60

4.3.2 Experimental Setup 61

4.4 Typical Results 62

4.4.1 Neutrons Experiments: A Contrast Variation Story 62

4.4.2 X-Ray Experiments: A Time-Resolved Story 67

4.5 Concluding Remarks 69

References 69

5 Differential Scanning Calorimetry of Polymers 72
Alejandro J. Müller and Rose Mary Michell

5.1 Introduction to Differential Scanning Calorimetry. Basic Principles and Types of DSC Equipment 72

5.2 Detection of First-Order and Second-Order Transitions by DSC. Applications of Standard DSC Experiments to the Determination of the Glass Transition Temperature and the Melting Temperature of Polymeric Materials 74

5.3 Self-Nucleation 75

5.3.1 Quantification of the Nucleation Efficiency 77

5.4 Thermal Fractionation 78

5.5 Multiphasic Materials: Polymer Blends and Block Copolymers. Fractionated Crystallization and Confinement Effects 81

5.5.1 Blends and Fractionated Crystallization 81

5.5.2 Copolymers 85

5.5.3 Copolymers Versus Blends 87

5.5.4 The Crystallization of Polymers and Copolymers within Nanoporous Templates 88

5.6 Self-Nucleation and the Efficiency Scale to Evaluate Nucleation Power 91

5.6.1 Supernucleation 93

5.7 Determination of Overall Isothermal Crystallization by DSC 95

5.8 Conclusions 95

Acknowledgment 95

References 95

6 Imaging Polymer Morphology using Atomic Force Microscopy 100
Holger Schönherr

6.1 Introduction 100

6.2 Fundamental AFM Techniques 101

6.2.1 Contact Mode AFM 101

6.2.2 Intermittent Contact (Tapping) Mode AFM 104

6.2.3 Further Dynamic AFM Modes 105

6.3 Imaging of Polymer Morphology 107

6.3.1 Single Polymer Chains 107

6.3.2 Crystal Structures 107

6.3.3 Lamellar Crystals 109

6.3.4 Spherulites 109

6.3.5 Multiphase Systems 109

6.3.6 Polymeric Nanostructures 111

6.4 Property Mapping 113

6.4.1 Nanomechanical Properties 113

6.4.2 Scanning Thermal Microscopy 115

References 115

7 FTIR Imaging of Polymeric Materials 118
S. G. Kazarian and K. L. A. Chan

7.1 Introduction 118

7.2 Principles of FTIR Imaging 118

7.3 Sampling Methods 120

7.3.1 Transmission Mode 120

7.3.2 Attenuated Total Reflection (ATR) Mode 121

7.4 Spatial Resolution 122

7.4.1 Transmission FTIR Imaging 123

7.4.2 ATR–FTIR Spectroscopic Imaging 123

7.5 Recent Applications 124

7.5.1 Polymer Blends 124

7.5.2 Polymer Processes 125

7.5.3 Polarized FTIR Imaging for Orientation Studies 126

7.6 Conclusions 127

References 128

8 NMR Analysis of Morphology and Structure of Polymers 131
Takeshi Yamanobe and Hiroki Uehara

8.1 Introduction 131

8.2 Basic Concepts in NMR 131

8.2.1 Principles of NMR 131

8.2.2 Analysis of the Free Induction Decay (FID) 132

8.3 Morphology and Relaxation Behavior of Polyethylene 134

8.3.1 Morphology and Molecular Mobility 134

8.3.2 Lamellar Thickening by Annealing 134

8.3.3 Entanglement in the Amorphous Phase 136

8.4 Morphology and Structure of the Nascent Powders 137

8.4.1 Etching by Fuming Nitric Acid 137

8.4.2 Structural Change by Annealing 138

8.4.3 Nascent Isotactic Polypropylene Powder 139

8.5 Kinetics of Dynamic Process of Polymers 141

8.5.1 Melt Drawing of Polyethylene 141

8.5.2 Crystallization Mechanism of Nylon 46 143

8.5.3 Degree of Curing of Novolac Resins 145

8.6 Conclusions 146

References 146

PART II MORPHOLOGY PROPERTIES AND PROCESSING 151

9 Small-Angle X-ray Scattering for Morphological Analysis of Semicrystalline Polymers 153
Anne Seidlitz and Thomas Thurn-Albrecht

9.1 Introduction 153

9.2 Small-angle X-ray Scattering 153

9.2.1 Typical Experimental Setup 153

9.2.2 Basic Formalism Describing the Relation between Real-Space Structure and Scattering Intensity in a SAXS Experiment 154

9.2.3 Methods of Analysis Used for SAXS on Semicrystalline Polymers 155

9.3 Concluding Remarks 162

Appendix: Calculation of the Model Function KÞ ′′ sim(s) 163

References 163

10 Crystalline Morphology of Homopolymers and Block Copolymers 165
Shuichi Nojima and Hironori Marubayashi

10.1 Introduction 165

10.2 Crystalline Morphology of Homopolymers 165

10.2.1 Crystal Structure 165

10.2.2 Lamellar Morphology 167

10.2.3 Spherulite Structure 168

10.2.4 Crystalline Morphology of Homopolymers Confined in Isolated Nanodomains 168

10.2.5 Crystalline Morphology of Polymer Blends 169

10.3 Crystalline Morphology of Block Copolymers 171

10.3.1 Crystalline Morphology of Weakly Segregated Block Copolymers 172

10.3.2 Crystalline Morphology of Block Copolymers with Glassy Amorphous Blocks 173

10.3.3 Crystalline Morphology of Strongly Segregated Block Copolymers 174

10.3.4 Crystalline Morphology of Double Crystalline Block Copolymers 175

10.4 Concluding Remarks 176

References 176

11 Isothermal Crystallization Kinetics of Polymers 181
Alejandro J. Müller Rose Mary Michell and Arnaldo T. Lorenzo

11.1 Introduction 181

11.2 Crystallization Process 182

11.3 Crystallization Kinetics 182

11.3.1 The Avrami Equation [31] 183

11.3.2 Nucleation and Crystal Growth: Lauritzen–Hofmann Theory 188

11.4 Isothermal Crystallization Kinetics–Morphology Relationship 191

11.4.1 Linear PS-b-PCL versus Miktoarm (PS2)-b-(PCL2) Block Copolymers 191

11.4.2 Crystallization Kinetics and Morphology of PLLA-b-PCL Diblock Copolymers 194

11.4.3 Nucleation and Crystallization Kinetics of Double Crystalline Polyethylene/Polyamide (PE/PA) Blends 196

11.4.4 Crystallization Kinetics of Poly(𝜀-Caprolactone)/Carbon Nanotubes (PCL/CNTs) Blends 200

11.5 Conclusions 201

Acknowledgments 201

References 201

12 Surface-induced Polymer Crystallization 204
Xiaoli Sun and Shouke Yan

12.1 Introduction 204

12.2 Influence of Foreign Surface on the Crystallization Kinetics of Polymers 205

12.3 Influence of Foreign Surface on the Crystal Structure and Morphology of Polymers 205

12.3.1 Crystallization of Thin Polymer Films on Amorphous Foreign Surface 205

12.3.2 Crystallization of Polymer Thin Films on Crystalline Foreign Surface with Special Crystallographic Interaction 209

12.4 Bulk Crystallization of Polymers in Contact with a Foreign Surface 226

12.5 Summary 234

References 235

13 Thermodynamics and Kinetics of Polymer Crystallization 242
Wenbing Hu and Liyun Zha

13.1 Introduction 242

13.2 Thermodynamics of Polymer Crystallization 242

13.3 Crystal Nucleation 247

13.4 Crystal Growth 251

13.5 Crystal Annealing 254

13.6 Summary 255

References 256

14 Self-Assembly and Morphology in Block Copolymer Systems with Specific Interactions 259
Anbazhagan Palanisamy and Qipeng Guo

14.1 Introduction 259

14.2 Block Copolymer Systems with Hydrogen Bonding Interaction in Solid State 260

14.2.1 Diblock Copolymer/Homopolymer Systems 260

14.2.2 Diblock/Triblock Copolymer Systems 264

14.3 Block Copolymer Systems with Hydrogen-Bonding Interaction in Solution 268

14.3.1 Single-Component Block Copolymer Systems 268

14.3.2 Diblock Copolymer/Homopolymer Systems 269

14.3.3 Diblock/Diblock Copolymer Systems 271

14.3.4 Triblock Copolymer Systems 275

14.4 Block Copolymer Systems with Ionic Interaction 275

14.4.1 Diblock Copolymer/Homopolymer Systems 275

14.4.2 Diblock/Triblock Copolymer Systems 276

14.5 Block Copolymer Blends via Metal–Ligand Coordination Bonds 278

14.6 Concluding Remarks 278

References 279

15 Dynamics Simulations of Microphase Separation in Block Copolymers 283
Xuehao He Xuejin Li Peng Chen and Haojun Liang

15.1 Introduction 283

15.2 Polymer Model and Simulation Algorithm 284

15.2.1 Monte Carlo Method 284

15.2.2 Dissipative Particle Dynamics Method 285

15.2.3 Polymeric Self-Consistent Field Theory 286

15.3 Dynamics of Self-Assembly of Block Copolymers 287

15.3.1 Phase Separation of Linear Block Copolymers 287

15.3.2 Self-Assembly of Star Block Copolymers in Melt 287

15.3.3 Self-Assembly of Block Copolymers in Constrained Systems 289

15.3.4 Micellization of Amphiphilic Block Copolymer in Solution 292

15.4 Outlook 294

References 295

16 Morphology Control of Polymer thin Films 299
Jiangang Liu Xinhong Yu Longjian Xue and Yanchun Han

16.1 Wetting 299

16.1.1 Dewetting Mechanisms 300

16.1.2 Dewetting Dynamics 301

16.1.3 Rim Instability 303

16.1.4 Factors Affecting the Stability of Polymer Thin Films 303

16.2 Thin Film of Polymer Blend 304

16.2.1 Fundamentals of Polymer Blends 305

16.2.2 Phase Separation in Thin Polymer Films 306

16.3 The Introduction of Polymer Blend Film in Solar Cells 307

16.3.1 Establish Interpenetrating Network Structure by Controlling Phase Separation 308

16.3.2 Control the Domain Size and Purify of the Domains 310

16.3.3 Adjust the Diffused Structure at the Interface Between Donor and Acceptor 312

16.3.4 Construct the Relationship Between Film Morphology and Device Performance 312

16.4 Summary and Outlook 313

References 313

17 Polymer Surface Topography and Nanomechanical Mapping 317
Hao Liu So Fujinami Dong Wang Ken Nakajima and Toshio Nishi

17.1 Introduction 317

17.2 Contact Mechanics 317

17.2.1 Hertzian Theory (Repulsion between Elastic Bodies) 318

17.2.2 Bradley Model (Interaction between Rigid Bodies) 318

17.2.3 Johnson–Kendall–Roberts (JKR) Model 318

17.2.4 Derjaguin–Muller–Toporov (DMT) Model 319

17.2.5 The JKR–DMT transition and Maugis–Dugdale (MD) Model 319

17.2.6 Adhesion Map 320

17.3 Application of Contact Mechanics to Experimental Data 321

17.3.1 Consideration of Contact Models 321

17.3.2 Force–Distance Curve Conversion 321

17.3.3 Analysis of Load–Indentation Curves 322

17.3.4 Nanomechanical Mapping 322

17.4 Application Examples 323

17.4.1 Effect of Processing Conditions on Morphology and Mechanical Properties of Block Copolymers 323

17.4.2 Measuring the Deformation of Both Ductile and Fragile Polymers 325

17.4.3 Nanorheological AFM on Rubbers 328

17.5 Conclusion 331

References 331

18 Polymer Morphology and Deformation Behavior 335
Masanori Hara

18.1 Introduction 335

18.2 Deformation Behavior of Amorphous Polymers 336

18.2.1 Deformation Behavior of Thin Films 336

18.2.2 Deformation Behavior of Bulk Polymers 338

18.3 Deformation Behavior of Semicrystalline Polymers 339

18.3.1 Deformation of Unoriented Semicrystalline Polymers 341

18.3.2 Strain Hardening and Network Density 341

18.4 Deformation Behavior of Block Copolymers 342

18.4.1 Block Copolymers Based on S and B 343

18.4.2 Block Copolymers Based on E and C (CHE) 345

18.5 Conclusions and Outlook 345

References 346

19 Morphology Development in Immiscible Polymer Blends 348
Ruth Cardinaels and Paula Moldenaers

19.1 Introduction 348

19.2 Morphology Development in Bulk Flow 350

19.2.1 Droplet–Matrix Structures 350

19.2.2 Fibrillar Structures 359

19.2.3 Cocontinuous Structures 361

19.3 Recent Advances in Polymer Blends 363

19.3.1 Immiscible Blends in Confined Flow 363

19.3.2 Blend Compatibilization by Nanoparticles 364

19.4 Conclusions 367

Acknowledgments 368

References 368

20 Processing Structure and Morphology in Polymer Nanocomposites 374
Duraccio Donatella Clara Silvestre Sossio Cimmino Antonella Marra and Marilena Pezzuto

20.1 Overview 374

20.2 Nanoparticles with One Dimension Less Than 100 nm (Layered Silicates) 375

20.3 Nanoparticles with Two Dimensions Less Than 100 nm (Carbon Nanotubes) 377

20.4 Nanoparticles with Three Dimensions Less Than 100 nm (Metal Metal Oxide) 380

20.5 Preparative Methods 382

20.5.1 Solution Processing 382

20.5.2 In situ Polymerization 383

20.5.3 Melt Processing 384

20.5.4 In situ Sol–Gel Technology 384

20.6 Structure and Morphology of Polymer Nanocomposites 385

20.7 Concluding Remarks 388

References 388

21 Morphology and Gas Barrier Properties of Polymer Nanocomposites 397
Abbas Ghanbari Marie-Claude Heuzey Pierre J. Carreau and Minh-Tan Ton-That

21.1 Introduction 397

21.2 Structure of Layered Silicates 397

21.3 Morphologies of Polymer-Layered Silicate Composites 398

21.4 Nanocomposite Preparation Methods 398

21.5 Challenges of Thermal Degradation in Melt Intercalation 400

21.6 Methods for Improving Gas Barrier Properties of Polymers 403

21.7 Polyamide Nanocomposites 405

21.8 Polyolefin Nanocomposites 405

21.9 Pet Nanocomposites 406

21.10 Polylactide Nanocomposites 413

21.11 Conclusions and Perspectives 414

References 415

22 Features on the Development and Stability of Phase Morphology in Complex Multicomponent Polymeric Systems: Main Focus on Processing Aspects 418
Charef Harrats Maria-Beatrice Coltelli and Gabriel Groeninckx

22.1 Introduction 418

22.2 Phase Morphology Development in Polymer Blends 419

22.2.1 Droplet-in-Matrix (Dispersed) Phase Morphology 419

22.2.2 Co-continuous Phase Morphology 419

22.2.3 Phase Morphology in Ternary Blends 420

22.3 Melt Processing of Polymer Blends 423

22.3.1 Morphology Buildup during Processing 423

22.3.2 Effects of Processing Parameters on Phase Morphology 424

22.4 Chemistry Involved in Polymer Blends 426

22.4.1 Effect of the Compatibilizer on Phase Morphology 426

22.4.2 Formation in situ of the Compatibilizer 427

22.4.3 Case of Reactive Ternary Blends 429

22.4.4 Stability of Phase Morphology in Reactively Compatibilized Blends 431

22.4.5 Organoclay-Promoted Phase Morphology 433

22.4.6 Conclusions 435

References 436

INDEX 439