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Book Details
Abstract
With tremendous growth over the last five years, mechanochemistry has become one of the most important topics in current polymer science research. With a particular focus on polymers and soft materials, Mechanochemistry in Materials looks at the subject from the application of macroscopic forces to solid systems of macroscopic dimensions.
The book has been divided according to length scale covering both experimental and theoretical considerations simultaneously. The first section of the book focuses on inspiration from nature, exploring and explaining multiple biological phenomena. The second section discusses molecular mechanochemistry, including the theoretical understanding of the transduction of mechanical force and its impact on covalent bonds cleavage and formation. The final section considers the implementation of these phenomena at the mesoscale and discusses the use of supramolecular/reversible aspects with similarities to biological systems.
The book provides a unique comparison with natural systems and contains all the important achievements in the area from the last decade. Appealing to a broad range of materials scientists, working in industry and academia, this well-presented and comprehensive title will be essential reading for researchers.
Table of Contents
| Section Title | Page | Action | Price |
|---|---|---|---|
| Cover | Cover | ||
| Mechanochemistry in Materials | i | ||
| Preface | vii | ||
| Contents | xi | ||
| Chapter 1 - Mechanochemistry: Inspiration from Biology | 1 | ||
| 1.1 Introduction and Historical Perspective | 1 | ||
| 1.2 Biomimetism and Rationale for Emulating Mechanotransduction Pathways | 3 | ||
| 1.2.1 Principles of Biomimetism and Strategies to Implement It | 3 | ||
| 1.2.2 Introduction of the Importance of Mechanotransduction Pathways for Living Organisms | 4 | ||
| 1.2.3 Adaptivity in Bones | 6 | ||
| 1.3 Sensing | 15 | ||
| 1.3.1 Via Protein Unfolding | 15 | ||
| 1.3.2 Via Ion Channel Opening | 21 | ||
| 1.4 Conclusion | 30 | ||
| References | 31 | ||
| Chapter 2 - Mechanophores for Chemical Function | 36 | ||
| 2.1 Introduction | 36 | ||
| 2.2 Creation of Reactive Species | 37 | ||
| 2.2.1 Radicals | 37 | ||
| 2.2.2 Carbon Cations | 38 | ||
| 2.2.3 Reactive Organic Functional Groups | 39 | ||
| 2.3 Catalyst Activation | 42 | ||
| 2.4 Spectral Change | 44 | ||
| 2.5 Production of Small Molecules | 47 | ||
| 2.6 Other | 48 | ||
| 2.7 Conclusions and Perspectives | 49 | ||
| References | 50 | ||
| Chapter 3 - Optical Sensing of Stress in Polymers | 53 | ||
| 3.1 Introduction | 53 | ||
| 3.2 Bond–Isomerization Reactions | 55 | ||
| 3.3 Covalent Bond Scission Reactions | 58 | ||
| 3.4 Conjugated Polymers | 63 | ||
| 3.5 Chromophore Rearrangement | 64 | ||
| 3.6 Photonic Polymers and Cholesteric Liquid Crystals | 67 | ||
| 3.7 Conclusion | 69 | ||
| Acknowledgements | 70 | ||
| References | 70 | ||
| Chapter 4 - Materials Design Principles for Mechanochemical Transduction | 76 | ||
| 4.1 Introduction | 76 | ||
| 4.2 Mechanics Terminology | 77 | ||
| 4.3 Mechanophore Kinetics | 79 | ||
| 4.4 Experimental Techniques for MCR Polymers | 82 | ||
| 4.5 Elastomers | 87 | ||
| 4.6 Glassy Polymers | 99 | ||
| 4.7 Composites and Coatings | 107 | ||
| 4.8 Mechanochemically Modified Networks | 108 | ||
| 4.9 Conclusions | 113 | ||
| Abbreviations | 114 | ||
| Acknowledgements | 115 | ||
| References | 115 | ||
| Chapter 5 - Tailoring Mechanochemical Reactivity of Covalent Bonds in Polymers by Non-covalent Interactions | 119 | ||
| 5.1 Introduction | 119 | ||
| 5.2 Theoretical Background of Polymer Mechanochemistry and the Effects of Supramolecular Interactions | 120 | ||
| 5.2.1 Coil-to-stretch Transition and Bead-rod Model | 120 | ||
| 5.2.2 Intra-chain Non-covalent Interactions | 121 | ||
| 5.2.2.1 Sacrificial Units to Delay Chain Extension | 122 | ||
| 5.2.2.2 Additional Hydrodynamic Shielding to Delay Chain Extension | 122 | ||
| 5.2.2.3 Reducing σmax at the Fully Extended State | 122 | ||
| 5.2.3 Inter-chain Non-covalent Interactions | 123 | ||
| 5.2.3.1 Linear Supramolecular Polymers | 123 | ||
| 5.2.3.2 Ladder-like Polymer Aggregates | 124 | ||
| 5.2.4 Non-covalent Interactions in the Bulk | 125 | ||
| 5.3 Experimental Observations | 125 | ||
| 5.3.1 Mechanical Cleavage of Covalent Bonds in Dilute Solution | 125 | ||
| 5.3.1.1 Shear Stability of Supramolecular Polymers and Aggregates in Drag Reduction | 125 | ||
| 5.3.1.2 Effect of Supramolecular Interactions on the Mechanochemical Reactivity of Disulfide Bond in Biomacromolecules | 127 | ||
| 5.3.2 Effects of Strong Hydrogen Bonding Interactions on the Activation of Mechanophores in the Bulk | 130 | ||
| 5.3.2.1 Polymers Containing Both Supramolecular Motifs and Mechanophores on the Backbone | 130 | ||
| 5.3.2.2 Mechanochemistry of SP in Soft and Hard Segments of PU | 131 | ||
| 5.3.2.3 Dioxetanes as Mechanoluminescent Probes in Thermoplastic Elastomers | 133 | ||
| 5.3.2.4 Mechanical Activation Enhanced by Strong Hydrogen Bonding at Chain Ends | 135 | ||
| 5.3.3 Effects of Van de Waals Interactions | 136 | ||
| 5.3.3.1 Activation of SP in Triblock Copolymer Thermoplastic Elastomers | 136 | ||
| 5.3.3.2 Tuning Non-covalent Interactions by Polymer Mechanochemistry | 138 | ||
| 5.3.4 Effect of Metallo-supramolecular Interactions | 140 | ||
| 5.3.4.1 Using Metal–ligand Complex as Mechanophores | 140 | ||
| 5.3.4.2 Effect of Metallo-supramolecular Interactions on the Activation of Mechanophores | 141 | ||
| 5.4 Non-covalent Interactions in Stress-responsive Materials | 143 | ||
| 5.4.1 Activation of Mechanophores and Irreversible Deformation of the Matrix | 143 | ||
| 5.4.2 Successive Mechanochemical Activation in Hydrogen-bonded Reinforced Elastomers | 143 | ||
| 5.5 Conclusions and Outlook | 146 | ||
| 5.5.1 Conclusions | 146 | ||
| 5.5.2 Outlook | 147 | ||
| Acknowledgements | 147 | ||
| References | 148 | ||
| Chapter 6 - Mechanochemistry of Polymer Brushes | 155 | ||
| 6.1 Introduction | 155 | ||
| 6.2 Degrafting of Polymer Brushes | 156 | ||
| 6.3 Summary and Conclusions | 164 | ||
| References | 165 | ||
| Chapter 7 - Coupling Mechanics to Chemical Reactions to Create “Materials that Compute” | 167 | ||
| 7.1 Introduction | 167 | ||
| 7.2 Modeling Self-oscillating Gels | 169 | ||
| 7.2.1 Kinetics of the BZ Reaction in a Polymer Gel | 169 | ||
| 7.2.2 Gel Swelling in the Presence of an External Force | 171 | ||
| 7.2.3 Values of Parameters Used in the Calculations | 172 | ||
| 7.3 Modeling Force-controlled Entrainment of BZ Gels | 173 | ||
| 7.3.1 Phase Dynamics Equations for Mechanically Deformed BZ Gels | 174 | ||
| 7.3.2 Entraining the Responsive BZ Gel | 176 | ||
| 7.4 Self-oscillating Gels Coupled Through Piezoelectric Films | 181 | ||
| 7.5 Conclusions | 191 | ||
| Acknowledgement | 192 | ||
| References | 192 | ||
| Subject Index | 194 |