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1 Shape Memory Polymers: Fundamentals, Advances and Applications Jinlian Hu SMITHERS R A P R A A Smithers Group Company Shawbury, Shrewsbury, Shropshire, SY4 4NR, United Kingdom Telephone: +44 (0) Fax: +44 (0)

2 ontents Shape-memory Polymers Introduction Shape-memory Effect Shape-memory Effect in Shape-memory Polymers Shape-memory Effect in Shape-memory Polymers and Shape-memory Alloys Structure of Shape-memory Polymers Thermally Induced Shape-memory Polymers Athermal Shape-memory Polymers Classification of Shape-memory Polymers Conclusions 17 Shape-memory Polymers: Molecular Design, Shape-memory Functionality and Programming Introduction Molecular Design of Shape-memory Polymers Thermally Sensitive Shape-memory Polymers Shape-memory Polymers based on the Amorphous Phase Shape-memory Polymers based on Semi-crystalline Phase Shape-memory Polymers based on Liquid Crystalline Phase Photosensitive Shape-memory Polymers Other Molecular Architectures of Shape-memory Polymers 28 vii

3 Shape Memory Polymers: Fundamentals, Advances and Applications 2.3 Shape-memory Programming Processing One-way Shape-memory Effects Dual-shape Creation Process for One-way Dual-shape Shape-memory Effects Programming for One-way Triple-shape Shape-memory Effects Processing Two-way Shape-memory Effects Programming for Two-way Dual-shape Shape-memory Effects Programming for Two-way Triple-shape Shape-memory Effects Multiple Shape-memory Effects Programming Shape-memory Functionality One-way Shape-memory Effects Two-way Shape-memory Effects Liquid Crystalline Elastomers Shape-memory Polymers having a Semi-crystalline Phase under Constant Stress Shape-memory Polymer Laminated Composites Triple/Multiple Shape-memory Effects Temperature-memory Effects Conclusions 48 3 Shape-memory Polymer Composites Introduction Nanowhisker/Shape-memory Polymer Composites Cellulose Nanowhiskers Integration of Cellulose Nanowhiskers Carbon/Shape-memory Polymer Composites Carbon Nanotube and Carbon Nanofibre/Shape-memory Polymer Composites 66

4 Contents Carbon Black/Shape-memory Polymer Composites Electrically Sensitive Shape-memory Polymer Nanocomposites Light-sensitive Shape-memory Polymer Nanocomposites Enhanced General Shape-memory Effect Fibre/Fabric-reinforced Shape-memory Polymer Composites Microfibre or Fabric/Shape-memory Polymer Composites Electrospun Nanofibre Shape-memory Polymer Nanocomposites Metal and Metal Oxides/Shape-memory Polymer Composites Other Shape-memory Polymer Composites Nanoclay/Shape-memory Polymer Composites Other Inorganic Filler/Shape-memory Polymer Composites Organic Filler/Shape-memory Polymer Composites Shape-memory Polymer Composites with Special Functions Conclusions 81 4 Shape-memory Polymer Blends Introduction Miscible Polymer Blends Shape-memory Polymer/Polymer Blends Amorphous Polymer/Crystalline Polymer Blends Immiscible Polymer Blends Elastomer/Polymer Blends Other Types of Immiscible Blends Blending and Post-crosslinking Polymers Networks Interpenetrating Polymer Networks Crosslinked Polymer Blends Conclusions 112 ix

5 Shape Memory Polymers: Fundamentals, Advances and Applications 5 Shape-memory Polymers Sensitive to Different Stimuli Introduction Thermally sensitive Shape-memory Polymers Shape-memory Effect based on Conventional Glass or Melting Transition Shape-memory Effect by Indirect Heating Shape-memory Effect based on a Thermally Reversible Reaction Shape-memory Effect based on Supermolecular Structure Two-way Shape-memory Effect based on Change in the Conformation of Anisotropic Chains Two-way Shape-memory Effect based on Coolinginduced Crystallisation Elongation Two-way Shape-memory Effect based on Shapememory Polymer/Carbon Nanotube Composites Multiple Shape-memory Effect based on Combined Switches Thermally active and ph-active Polymeric Hydrogels Light-sensitive Shape-memory Polymers Photodeformability Induced by Photoisomerisation Photodeformability induced by Photoreactive Molecules Photoactive Effect from the Addition-fragmentation Chain Transfer Reaction Light-active Polymeric Hydrogels Magnetic-sensitive Shape-memory Polymers Shape-memory Polymer Matrices filled with Magnetic Particles Magnetic-active polymeric gels Water/solvent-sensitive Shape-memory Polymers Electric-sensitive Shape-memory Polymers Conclusions 148 x

6 Contents Modelling of Shape-memory Polymers Introduction Macroscale Constitutive Modelling Stress-strain Characteristics Shape-memory Properties Mesoscale Modelling Microscale Modelling Molecular Dynamics and Monte Carlo Simulations Reaction Characteristics Physical Properties Microstructure Hydrogen bonding Interactions Mechanical Properties Mathematical Modelling Modelling of Device Structures Modelling for Light-sensitive Shape-memory Polymers Three-dimensional Finite Deformation Modelling Multiple Natural Configurations Modelling Multi-scale Modelling Conclusions 183 Supramolecular Shape-memory Polymers Introduction Supramolecular Chemistry Hydrogen Bonding Relationship between Shape-memory Polymers and Supramolecular Polymer Networks Polymers Containing Pyridine Moieties: a Pathway to Achieve Supramolecular Networks Function of Pyridine Moieties in Supramolecular Chemistry 194 XI

7 Shape Memory Polymers: Fundamentals, Advances and Applications Supramolecular Pyridine-containing Polymers Supramolecular Liquid Crystalline Polymer-containing Pyridine Moieties Supramolecular Shape-memory Polymers based on Pyridine Moieties Synthesis Structure and Morphology Thermally induced Shape-memory Effect Moisture-sensitive Shape-memory Effect Supramolecular Shape-memory Polymers based on Cyclodextrins Cyclodextrins Thermally induced Shape-memory Effect Non-thermally Induced Shape-memory Effects Potential Applications Reshape Applications Shape-memory Effect for Hairstyles in Beauty Care Two-way Shape-memory Polymer Laminates Medical Application: Antibacterial Intelligent Windows for Smart Textile Applications Conclusions Applications of Shape-memory Polymers Introduction Applications of Bulk Shape-memory Polymers Fixation Orthodontic Wires Medical Casts Actuation Actuation Realised by Combining Shapememory Polymers with Specific Structures 226 xn

8 Contents Actuation arising from a Two-way Shapememory Effect Deployment Cold Hibernated Elastic Memory of Shapememory Polymer Foams Expandable Stents Deployable Dialysis Needles, Coils and Neuronal Electrodes Self-healing Confined Shape-recovery Self-healing Fitting Applications in Surface Wrinkling and Patterning Principe of Surface Wrinkling Wetting and Spreading Adaptable Biological Devices for Modulating Cellularsubstrate Interactions Biosensor and Micro-systems Programmable Surface Pattern No-programming Reversible Shape-memory Surface Patterns Applications in Textiles Shape-memory Polymer Fibres Shape-memory Polymer Yarns and Fabrics Shape-memory Polymer Solutions for Finishing Fabrics Shape-memory Polymer Nanofibres and their Nonwovens Shape-memory Polymer Film/Foam and Laminated Textiles Engineering Applications Transportation Sensors and Actuators Filtration 251 xiii

9 Shape Memory Polymers: Fundamentals, Advances and Applications Insulation Conclusions Future Outlook Introduction New Shape-memory Polymers with Novel Structures and Diversified Functionalities New Stimulus Switches Intrinsic Athermal Switches Multi-responsive and Multi-functional Switches Development Trends of Shape-memory Polymer Composites and Blends Electric-Sensitive Shape-memory Effect Light-Sensitive Shape-memory Effect Magnetic-Sensitive Shape-memory Effect Water/Solvent-Sensitive Shape-memory Effect Shape-memory Effect based on Non-thermal Phase Transitions Versatile Shape-memory Effects by Novel Programming Protocols Programmability Imperfection or a New Shape-memory Effect Fundamental Understanding Comprehensive Study of Structure-property Relationships Modelling Application in Textiles Biomedical Applications Applications toward Commercial Success Maturing and Broadening of Applications Existing Widely Researched Areas Broadening Areas 275 xiv

10 Contents Untouched Areas Integrated Approaches Challenging Issues in Applications Supramolecular Shape-memory Polymers Conclusions 279 Abbreviations 285 Index 295 xv

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