Thermal Analysis of Polymers

• Presents a solid introduction to thermal analysis, methods, instrumentation, calibration, and application along with the necessary theoretical background.
• Useful to chemists, physicists, materials scientists, and engineers who are new to thermal analysis techniques, and to existing users of thermal analysis who wish expand their experience to new techniques and applications
• Topics covered include Differential Scanning Calorimetry and Differential Thermal Analysis (DSC/DTA), Thermogravimetry, Thermomechanical Analysis and Dilatometry, Dynamic Mechanical Analysis, Micro-Thermal Analysis, Hot Stage Microscopy, and Instrumentation.
• Written by experts in the various areas of thermal analysis
• Relevant and detailed experiments and examples follow each chapter.

Preface ix

1 Introduction 1
Joseph D. Menczel, R. Bruce Prime and Patrick K. Gallagher

2 Differential Scanning Calorimetry (DSC) 7
Joseph D. Menczel, Lawrence Judovits, R. Bruce Prime, Harvey E. Bair, Mike Reading, and Steven Swier

2.1. Introduction 7

2.2. Elements of Thermodynamics in DSC 9

2.3. The Basics of Differential Scanning Calorimetry 18

2.4. Purity Determination of Low-Molecular-Mass Compounds by DSC 37

2.5. Calibration of Differential Scanning Calorimeters 41

2.6. Measurement of Heat Capacity 52

2.7. Phase Transitions in Amorphous and Crystalline Polymers 58

2.8. Fibers 115

2.9. Films 123

2.10. Thermosets 130

2.11. Differential Photocalorimetry (DPC) 154

2.12. Fast-Scan DSC 162

2.13. Modulated Temperature Differential Scanning Calorimetry (MTDSC) 168

2.14. How to Perform DSC Measurements 208

2.15. Instrumentation 217

Appendix 225

Abbreviations 225

References 229

3 Thermogravimetric Analysis (TGA) 241
R. Bruce Prime, Harvey E. Bair, Sergey Vyazovkin, Patrick K. Gallagher, and Alan Riga

3.1. Introduction 241

3.2. Background Principles and Measurement Modes 242

3.3. Calibration and Reference Materials 251

3.4. Measurements and Analyses 256

3.5. Kinetics 277

3.6. Selected Applications 295

3.7. Instrumentation 308

Appendix 311

Abbreviations 312

References 314

4 Thermomechanical Analysis (TMA) and Thermodilatometry (TD) 319
Harvey E. Bair, Ali E. Akinay, Joseph D. Menczel, R. Bruce Prime, and Michael Jaffe

4.1. Introduction 319

4.2. Principles and Theory 320

4.3. Instrumental 326

4.4. Calibration 332

4.5. How to Perform a TMA Experiment 335

4.6. Key Applications 340

4.7. Selected Industrial Applications (with Details of Experimental Conditions) 363

Appendix 378

Abbreviations 380

References 381

5 Dynamic Mechanical Analysis (DMA) 387
Richard P. Chartoff, Joseph D. Menczel, and Steven H. Dillman

5.1. Introduction 387

5.2. Characterization of Viscoelastic Behavior 394

5.3. The Relationship between Time, Temperature, and Frequency 401

5.4. Applications of Dynamic Mechanical Analysis 410

5.5. Examples of DMA Characterization for Thermoplastics 424

5.6. Characteristics of Fibers and Thin Films 432

5.7. DMA Characterization of Crosslinked Polymers 438

5.8. Practical Aspects of Conducting DMA Experiments 456

5.9. Commercial DMA Instrumentation 477

Appendix 488

Abbreviations 489

References 491

6 Dielectric Analysis (DEA) 497
Aglaia Vassilikou-Dova and Ioannis M. Kalogeras

6.1. Introduction 497

6.2. Theory and Background of Dielectric Analysis 502

6.3. Dielectric Techniques 520

6.4. Performing Dielectric Experiments 528

6.5. Typical Measurements on Poly(Methyl Methacrylate) (PMMA) 538

6.6. Dielectric Analysis of Thermoplastics 553

6.7. Dielectric Analysis of Thermosets 576

6.8. Instrumentation 592

Appendix 599

Abbreviations 599

References 603

7 Micro- And Nanoscale Local Thermal Analysis 615
Valeriy V Gorbunov, David Grandy, Mike Reading, and Vladimir V. Tsukruk

7.1. Introduction 615

7.2. The Atomic Force Microscope 616

7.3. Scanning Thermal Microscopy 618

7.4. Thermal Probe Design and Spatial Resolution 620

7.5. Measuring Thermal Conductivity and Thermal Force-Distance Curves 624

7.6. Local Thermal Analysis 628

7.7. Performing a Micro/Nanoscale Thermal Analysis Experiment 633

7.8. Examples of Micro/Nanoscale Thermal Analysis Applications 637

7.9. Overview of Local Thermal Analysis 644

Abbreviations 647

References 648

Index 651

"I have read it with great pleasure and it is my honor to provide this short review. Let me congratulate the editors on the concept of this book. They managed to tune the balance between basic principles and practical information finely . . .In conclusion I think that this book is very useful for students, PhDs, and researchers who are dealing or intended to deal with thermal analysis of polymers." (J Therm Anal Calorim, 2010)

Joseph D. Menczel, PhD, a recognized expert in thermal analysis of polymers with some thirty years of industrial and academic experience, is Assistant Technical Director at Alcon Laboratories. He has researched more than 120 polymeric systems in which he studied calibration of DSCs, glass transition, nucleation, crystallization, melting, stability, mechanical and micro-mechanical properties of polymers, and polymer-water interactions. Dr. Menczel holds six patents and is the author of seventy scholarly papers. He is the author of two chapters in the bookThermal Characterization of Polymeric Materials. In conducting DSC experiments, Dr. Menczel found a crystal/amorphous interface in semicrystalline polymers, which later became known as the rigid amorphous phase. He is also credited with developing the temperature calibration of DSCs for cooling experiments.

R. Bruce Prime, PhD, is a consultant to industry and government and a recognized authority on the cure and properties of cross-linked polymer systems. During his thirty-year career with IBM, he led teams responsible for developing and implementing polymer applications for printer and information storage technologies. He holds four patents and is the author of more than fifty technical papers and the chapter on thermosets in Thermal Characterization of Polymeric Materials. Dr. Prime is a Fellow of SPE and NATAS and was the 1989 recipient of the Mettler-Toledo Award in Thermal Analysis. He maintains the Web site www.primethermosets.com.

Learn how to take full advantage of a broad range of thermal analysis techniques

Thermal Analysis of Polymers: Fundamentals and Applications emphasizes the practical uses of thermal analysis, enabling readers to take full advantage of its capabilities as a polymer characterization tool in their laboratories. The book offers essential theoretical background; however, it focuses on how to perform a broad range of thermal analysis measurements and tests, with detailed coverage of methods, applications, instrumentation, and calibration. Moreover, it helps readers correctly interpret their results.

This book features a team of authors whose expertise spans all the thermal analysis techniques and applications covered in the book. Their advice is based not only on thorough knowledge of the literature, but also their own hands-on experience working in the lab. Among the topics covered are:

• Differential scanning calorimetry

• Thermogravimetric analysis

• Thermomechanical analysis and thermodilatometry

• Dynamic mechanical analysis

• Dielectric analysis

• Micro- and nano-scale local thermal analysis

Each chapter guides readers through the applications of thermal analysis for polymer char-acterization, with detailed examples that show how to perform each step. References guide readers to the primary literature for further investigation into each topic.

Following this book's step-by-step guidance, chemists and engineers new to thermal analysis techniques, whether in industry, government, or academia, can quickly learn to use them to generate high-quality results. For more experienced researchers, the book enables them to expand their repertoire to include a broader range of sophisticated techniques and applications.