Nonlinear Dynamics with Polymers: Fundamentals, Methods and Applications

Nonlinear Dynamics with Polymers: Fundamentals, Methods and Applications......Page 5
Contents......Page 7
List of Contributors......Page 13
1.1 Overview......Page 17
1.2 What Follows......Page 18
References......Page 20
2.2 Nonlinear Dynamics......Page 21
2.3 Some Key Ideas of Nonlinear Chemical Dynamics......Page 22
2.3.2 Waves and Patterns......Page 23
2.3.3 More Complex Phenomena......Page 24
2.4 Polymeric Systems......Page 25
2.4.3 Sources of Feedback......Page 26
2.4.4 Nonlinear Dynamics and Phase Separation of Reacting Systems......Page 28
2.4.6 Approaches to Nonlinear Dynamics in Polymeric Systems......Page 29
References......Page 32
3.1 Introduction......Page 37
3.2.1 The Relationship between Nonlinear Rheology and the Extent of Polymerization during the Growth of Linear Chains......Page 38
3.2.2 Relationship between Nonlinear Rheology and the Extent of Polymerization during the Growth of Nonlinear Chains......Page 40
3.2.3 Chemical Structure of the Monomers and Polymerization Mechanism in Polyurethane Polymerization......Page 41
3.2.4 Evolution of Nonlinear Rheology during Polyurethane Polymerization......Page 42
3.3 Evolution of Nonlinear Rheology and Network Formation during Thermoplastic Polyurethane Polymerization: Effects of Mixer Design, Mixing Protocol, Catalyst Concentration, and Timescales......Page 43
3.3.1.1 Mechanism of Mixing......Page 45
3.3.1.3 Dispersive and Distributive Mixing......Page 46
3.3.1.4 Chaotic Mixing......Page 47
3.3.2 Analysis of Timescale of Mixing and Chemical Reactions during TPU Polymerization......Page 48
3.3.3 Simultaneous Effects of Mixing, Chemical Reaction, and Molecular Diffusion on the Evolution of Nonlinear Rheological Properties......Page 52
3.4 Conclusions......Page 54
References......Page 56
4.1.1 Requirements for Frontal Polymerizations......Page 61
4.1.2 Types of Systems......Page 62
4.1.3 Characteristics of Frontal Polymerization......Page 63
4.2.1 Cure-On-Demand Putty......Page 65
4.2.2 Adhesive......Page 66
4.3 Motivation for Studying Nonlinear Dynamics with Frontal Polymerization......Page 67
4.4.1 Buoyancy-Driven Convection......Page 68
4.4.2 Effect of Surface-Tension-Driven Convection......Page 71
4.5 Thermal Instabilities......Page 72
4.5.1 Effect of Complex Kinetics......Page 73
4.5.2 Effect of Bubbles......Page 74
4.6 Snell’s Law......Page 75
4.7 Three-Dimensional Frontal Polymerization......Page 76
4.8 Impact on Applications......Page 77
References......Page 78
5.1.1 A Comparison between TFP and IFP: Their Mechanisms and Front Properties......Page 85
5.1.2 Background......Page 87
5.2 Mathematical Models......Page 90
5.3 Experimental IFP......Page 95
5.4 Comparison of Experimental and Mathematical IFP......Page 101
5.5 Conclusions......Page 103
References......Page 104
6.1 Introduction......Page 107
6.2.1 Phase Separation of Nonreacting Mixtures......Page 108
6.2.2 Phase Separation of Reacting Mixtures......Page 110
6.3.1 Reaction Kinetics in the Bulk State of Polymer......Page 113
6.3.2 Reaction Kinetics in the Liquid State of Polymer Mixtures......Page 114
6.4 Reaction-Induced Elastic Strain and Its Relaxation Behavior......Page 115
6.5.1 Polymers with Spatially Graded Continuous Structures......Page 117
6.5.2.1 The Computer-Assisted Irradiation Method......Page 121
6.5.2.2 Polymers with an Arbitrary Distribution of Characteristic Length Scales......Page 122
6.6 Conclusions......Page 125
References......Page 126
7.1 Introduction......Page 131
7.2 Design of Self-Oscillating Gel......Page 132
7.3.1 Self-Oscillation of the Miniature Bulk Gel......Page 133
7.3.3 Peristaltic Motion of Gels with Propagation of Chemical Wave......Page 135
7.3.4 Self-Oscillation with Structural Color Changes......Page 137
7.4.1 Self-Walking Gel......Page 138
7.4.3 Microfabrication of Self-Oscillating Gel for Microdevices......Page 140
7.4.4 Control of Chemical Wave Propagation in Self-Oscillating Gel Array......Page 142
7.4.5 Self-Oscillating Polymer Chains as ‘‘Nano-Oscillators’’......Page 143
7.4.6 Self-Flocculating/Dispersing Oscillation of Microgels......Page 144
7.4.7 Fabrication of Microgel Beads Monolayer......Page 145
7.4.8 Attempts of Self-Oscillation under Physiological Conditions......Page 147
References......Page 148
8.1 Introduction......Page 151
8.2.1 Continuum Equations......Page 153
8.2.2 Formulation of the Gel Lattice Spring Model (gLSM)......Page 156
8.3.1 Capturing Effects of Local Mechanical Impact on Homogeneous BZ Gels......Page 159
8.3.2 Straining Heterogeneous BZ Gels......Page 163
8.4 Sensitivity to Light......Page 170
Acknowledgments......Page 176
References......Page 177
9.1 Introduction......Page 179
9.2 Elastodynamics of Responsive Gels: a Brief Survey......Page 180
9.3.1 The Approach......Page 182
9.3.2 Coupling to the Oscillating Belousov–Zhabotinsky Reaction......Page 185
9.3.3 Numerical Integration Results......Page 187
9.4.1 Spatial Bistability and Related Chemomechanical Instabilities......Page 190
9.4.2 Simple Models......Page 191
9.4.3 A More Realistic Model: The Polyelectrolyte Model......Page 193
9.5 Experimental Observations......Page 197
9.5.1.1 Case of the Chlorite–Tetrathionate Reaction......Page 198
9.5.1.2 Case of the Bromate–Sulfite Reaction......Page 200
9.6 Conclusions and Perspectives......Page 201
References......Page 202
10.1 Introduction......Page 205
10.2.1 Teorell Oscillator......Page 207
10.2.2 Polyelectrolyte Membrane-Based Oscillators......Page 209
10.2.3 Thermofluidic Oscillator......Page 210
10.2.5 Membrane/Enzyme Oscillators......Page 212
10.2.6 General Discussion......Page 214
10.3 Hydrogel–Enyzme Oscillator for Rhythmic Hormone Delivery......Page 215
10.3.1 General Scheme......Page 216
10.3.2 Bistability of Hydrogel Membrane Permeability......Page 217
10.3.3 Oscillator Operation......Page 220
10.3.4 Oscillator Prototype......Page 221
10.3.5 Analysis of Factors Affecting Oscillations Over Time......Page 223
10.3.6 Tuning pH Range of Oscillations......Page 224
10.3.7 Discussion and Conclusion......Page 227
References......Page 228
Further Reading......Page 233
11.1 Introduction......Page 235
11.2 Permanent Patterns from Inorganic Precipitation and Deposition Processes......Page 236
11.3 Tube Formation in Precipitation Systems and Silica Gardens......Page 237
11.4 Historic and Cultural Links......Page 238
11.5 Some Recent Developments......Page 239
11.6 Experimental Methods......Page 240
11.7 Growth Regimes......Page 241
11.8 Wall Composition and Morphology......Page 244
11.9 Relaxation Oscillations......Page 246
11.10 Radius Selection......Page 249
11.11 Bubbles as Templates......Page 251
11.12 Toward Applications......Page 253
11.13 Outlook and Conclusions......Page 254
References......Page 255
Index......Page 259