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Reactions and Mechanisms in Thermal Analysis of Advanced Materials

ISBN: 978-1-119-11757-5
616 pages
August 2015
Reactions and Mechanisms in Thermal Analysis of Advanced Materials (1119117577) cover image

Description

Strong bonds form stronger materials. For this reason, the investigation on thermal degradation of materials is a significantly important area in research and development activities. The analysis of thermal stability can be used to assess the behavior of materials in the aggressive environmental conditions, which in turn provides valuable information about the service life span of the materiel.

Unlike other books published so far that have focused on either the fundamentals of thermal analysis or the degradation pattern of the materials, this book is specifically on the mechanism of degradation of materials.

The mechanism of rapturing of chemical bonds as a result of exposure to high-temperature environment is difficult to study and resulting mechanistic pathway hard to establish. Limited information is available on this subject in the published literatures and difficult to excavate.

Chapters in this book are contributed by the experts working on thermal degradation and analysis of the wide variety of advanced and traditional materials. Each chapter discusses the material, its possible application, behavior of chemical entities when exposed to high-temperature environment and mode and the mechanistic route of its decomposition. Such information is crucial while selecting the chemical ingredients during the synthesis or development of new materials technology.

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Table of Contents

Preface xv

Part 1: Degradation of Polymers

1 Thermal Stability of Organic Monolayers Covalently Grafted on Silicon Surfaces 3
Florent Yang, Philippe Allongue, Francois Ozanam and Jean-Noel Chazalviel

1.1 Introduction 3

1.2 Alkyl-Grafted Surfaces 8

1.3 Alkoxy-Grafted Surfaces 15

1.4 Surfaces Grafted with Aryl Groups 19

1.5 Surfaces Grafted via Si–N Linkages 22

1.6 Summary 27

References 30

2 Thermal Analysis to Discriminate the Stability of Biomedical Ultrahigh-Molecular-Weight Polyethylenes Formulations 39
Maria Jose Martinez-Morlanes and Francisco Javier Medel

2.1 Introduction 39

2.2 Suitability of TGA Analysis for the Study of Stability of Medical Polyethylene 42

2.3 Activation Energies of Degradation Processes in the Thermal Decomposition of UHMWPE 56

References 58

3 Materials Obtained by Solid-State Thermal Decomposition of Coordination Compounds and Metal–Organic Coordination Polymers 63
Oana Carp

3.1 Introduction 63

3.2 Coordination Compounds and Metal–Organic Coordination Polymers as Precursors of Oxides 65

3.3 Coordination Compounds and Metal–Organic Coordination Polymers as Precursors of Sulfides 72

3.4 Coordination Compounds as Precursors of Composites 74

3.5 Coordination Compounds and Metal–Organic Coordination Polymers as Precursors of New Complexes 74

3.6 Coordination Compounds and Metal–Organic Coordination Polymers as Precursor of Metals 75

3.7 Coordination Compounds as Precursor of Nitrides 76

3.8 Other Materials 77

3.9 Conclusions 77

References 78

4 Methods for Limiting the Flammability of High-Density Polyethylene with Magnesium Hydroxide 85
Joanna Lenża, Maria Sozańska and Henryk Rydarowski

4.1 Introduction 85

4.2 Experimental Part 88

4.3 Results and Discussion 91

4.4 Conclusions 99

References 100

5 Thermal Analysis in the Study of Polymer (Bio)-degradation 103
Joanna Rydz, Marta Musioł and Henryk Janeczek

5.1 Introduction 103

5.2 Differential Scanning Calorimetry 105

5.3 Dynamic Mechanical Analysis 112

5.4 Thermogravimetric Analysis 115

5.5 Conclusions 120

Acknowledgments 121

References 121

6 Thermal and Oxidative Degradation Behavior of Polymers and Nanocomposites 127
Gauri Ramasubramanian and Samy Madbouly

6.1 Introduction 127

6.2 Thermal Degradation 131

6.3 Chemical and Oxidative Degradation 137

6.4 Photo-oxidation 143

6.5 Environmental and Biological Degradation 148

6.6 Degradation of Polymer Nanocomposites 154

6.7 Conclusions 162

References 162

7 Thermal Degradation Effects on Polyurethanes and Their Nanocomposites 165
Ivan Navarro-Baena, Marina P. Arrieta, Alicia Mujica-Garcia, Valentina Sessini, Jose M. Kenny and Laura Peponi

7.1 Introduction 165

7.2 Main Techniques Used for Studying the Thermal Degradation Process 167

7.3 Degradation Mechanisms 169

7.4 Chemical Approaches Used to Improve the Thermal Stability of PU 171

7.5 Thermal Degradation of PU Based on Natural Sources 172

7.6 Nanocomposites 174

7.7 PU Electrospun Fibers 181

7.8 Conclusions 184

References 184

8 Controllable Thermal Degradation of Thermosetting Epoxy Resins 191
Zhonggang Wang

8.1 Introduction 191

8.2 Ester-, Carbamate-, and Carbonate-Linked Reworkable Epoxy Resins 193

8.3 Ether-Linked Reworkable Epoxy Resins 195

8.4 Phosphate- and Phosphite-Linked Reworkable Epoxy Resins 196

8.5 Sulfite-Linked Reworkable Epoxy Resins 204

References 207

9 Mechanism of Thermal Degradation of Vinylidene Chloride Barrier Polymers 209
Bob A. Howell

9.1 Introduction 209

9.2 Discussion 210

9.3 Conclusions 218

References 219

10 Role of Mass Spectrometry in the Elucidation of Thermal Degradation Mechanisms in Polymeric Materials 221
Paola Rizzarelli and Sabrina Carroccio

10.1 Introduction 221

10.2 Thermogravimetry-Mass Spectrometry (TG-MS) 224

10.3 Gas Chromatography-Mass Spectrometry (GC-MS) and Pyrolysis-Gas Chromatography/Mass Spectrometry (Py-GC/MS) 228

10.4 Direct Pyrolysis Mass Spectrometry (DPMS) 237

10.5 Matrix-Assisted Laser Desorption Ionisation Mass Spectrometry (MALDI MS) 242

10.6 Other Mass Spectrometric Techniques 246

10.7 Conclusions 249

References 251

11 The Mechanism of Poly(styrene) Degradation 259
Bob A. Howell

11.1 Introduction 259

11.2 Discussion 260

11.3 Conclusions 266

References 266

12 The Use of Thermal Volatilization Analysis of Polylactic Acid and Its Blends with Starch 269
Derval dos Santos Rosa, Claudio Roberto Passatore, and Jose Ricardo Nunes de Macedo

12.1 Introduction 269

12.2 Use of TVA 271

12.3 TVA as an Analytic Technique 272

12.4 TVA-PLA Investigation 274

12.5 TVA – Thermoplastic Starch 276

12.6 Analyses of TVA – PLA and Their Mixtures with Thermoplastic Starch 280

12.7 Conclusions 282

Acknowledgments 282

References 282

Part 2: Degradation of Other Materials

13 Reaction Mechanisms in Thermal Analysis of Amazon Oilseeds 287
Orquidea Vasconcelos dos Santos, Carlos Emmerson and Suzana Caetano da Silva Lannes

13.1 Introduction 287

13.2 Oxidative Stability 297

References 299

14 Thermal Degradation of Cellulose and Cellulosic Substrates 301
Jenny Alongi and Giulio Malucelli

14.1 Introduction 301

14.2 Thermal and Thermo-oxidative Degradation of Cellulose 302

14.3 Factors Affecting Cellulose Thermal Degradation: Charring/Volatilisation Competition 318

14.4 Conclusions 329

References 330

15 Thermal Decomposition Behavior of Sodium Alkoxides of Relevance to Fast Reactor Technology 333
K. Chandran, M. Kamruddin, S. Anthonysamy and V. Ganesan

15.1 Introduction 333

15.2 Preparation of Sodium Alkoxides 334

15.3 Characterization of Sodium Alkoxides 339

15.4 Thermal Decomposition of Sodium Alkoxides 348

15.5 Kinetic Analysis 364

References 390

16 Thermal Degradation and Morphological Characteristics of Bone Products 393
F. Miculescu, A. Maidaniuc, G.E. Stan, M. Miculescu, S.I. Voicu, L.T.Ciocan

16.1 Introduction and Objectives 393

16.2 Short Overview on the Thermal Analysis Experimental Methods 396

16.3 Morpho-structural Changes Induced by the Thermal Treatments Applied to Hard Tissues. Bone Degradation Mechanism 400

16.4 Conclusions 408

References 408

17 Processes and Mechanisms in Hydrothermal Degradation of Waste Electric and Electronic Equipment 411
Yu Luling, He Wenzhi and Li Guangming

17.1 Introduction 411

17.2 Application of Hydrothermal Degradation in Treatment of WEEE 414

17.3 Mechanism of Hydrothermal Degradation for Treatment of WEEE 418

17.4 Conclusion 431

Acknowledgements 431

References 431

18 Heat Transfer Mechanism and Thermomechanical Analysis of Masonry Structures (Mortars and Bricks) Subjected to High Temperatures 437
M.E. Macia Torregrosa and J. Camacho Diez

18.1 Introduction: State of the Art 437

18.2 Heat Transfer Mechanisms through a Masonry Element under Load 442

18.3 Influence of High Temperatures on the Structural Behavior of a Masonry Element 444

18.4 Factors Involved in the Behavior of the Masonry Subjected to High Temperatures 444

18.5 Properties of the Ceramic Pieces 449

18.6 Properties of the Mortar 456

References 463

19 Application of Vibrational Spectroscopy to Elucidate Protein Conformational Changes Promoted by Thermal Treatment in Muscle-Based Food 467
A.M. Herrero, P. Carmona, F. Jimenez-Colmenero and C. Ruiz-Capillas

19.1 Introduction 467

19.2 Protein Structure 468

19.3 Muscle-Based Food Proteins: Thermal treatment 468

19.4 Vibrational Spectroscopic Methods and Protein Structure 469

19.5 Vibrational Spectroscopy to Elucidate Structural Changes Induced by Thermal Treatment in Muscle Foods 473

19.6 Conclusions 479

Acknowledgements 479

References 480

20 Thermal Activation of Layered Hydroxide-Based Catalysts 483
Milica Hadnadjev-Kostic, Tatjana Vulic and Radmila Marinkovic-Neducin

20.1 Introduction 483

20.2 LDH General Properties 484

20.3 Thermal Activation of LDH-Based Catalysts – Thermal Decomposition Pathway from LDH to Mixed Oxides 490

20.4 Properties of Thermally Activated LDHs 495

20.5 Application of LDH-Based Materials 501

20.6 Synthesis Methods of Ti-Containing LDH-Based Materials 502

20.7 Synthesis Methods for the Association of TiO2 and LDH-Based Catalysts 502

20.8 Conclusions and Perspectives 509

References 510

21 Thermal Decomposition of Natural Fibers: Kinetics and Degradation Mechanisms 515
Matheus Poletto, Heitor L. Ornaghi Junior and Ademir J. Zattera

21.1 Introduction 515

21.2 Theoretical Background 516

21.3 Chemical Composition of the Natural Fibers 522

21.4 XRD Analysis Applied to Natural Fibers 524

21.5 Thermogravimetric Analysis of Natural Fibers 527

21.6 Kinetic Degradation and Reaction Mechanisms in the Solid State of Natural Fibers 532

21.7 Conclusion 541

References 541

22 On the Kinetic Mechanism of Non-isothermal Degradation of Solids 547
Lyubomir T. Vlaev, Velyana G. Georgieva, and Mariana P. Tavlieva

22.1 Introduction 547

22.2 Mathematical Background in the Thermogravimetry 549

22.3 Kinetic Mechanism of the Thermal Degradation of CaC2O4・H2O 561

22.4 Kinetic Mechanism of the Thermal Degradation of Chitin 567

22.5 Kinetic Mechanism of the Thermal Degradation of Rice Husks 571

22.6 Conclusions 574

Acknowledgments 575

References 575

Index 579

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