ISBN: 3-540-65487-9
TITLE: Polymer Sensors and Actuators
AUTHOR: Osada, Yoshihito; De Rossi, Danilo E. (Eds.)
TOC:

Chapter 1 
Ion Conducting Polymer Sensors 
Y. Sakai 
1.1 Introduction 1 
1.2 Humidity Sensors 1 
1.2.1 Humidity Sensors Using Polymers Containing Inorganic Salts 1 
1.2.2 Humidity Sensors Using Polymer Electrolytes 2 
1.2.2.1 Electrolyte Homopolymers 2 
1.2.2.2 Copolymers 4 
1.2.2.3 Graft Copolymers 5 
1.2.2.4 Hydrophobic Polymers With Added Ionic Groups 7 
1.2.2.5 Crosslinked Polymer Electrolytes 8 
1.3 Gas Sensors 10 
References 12 
Chapter 2 
Ultrathin Films for Sensorics and Molecular Electronics 
L. Brehmer 
2.1 Molecular Electronics and Nanosensorics 15 
2.2 Ultrathin Films and Supramolecular Architectures 18 
2.2.1 State of the Art 18 
2.2.2 Langmuir- and Langmuir-Blodgett Films: Formation and Structure 
Investigation 19 
2.2.2.1 Langmuir Films 19 
2.2.2.2 Formation of Langmuir-Blodgett Films 22 
2.2.2.3 Structure Investigation of LB-Films 24 
2.3 Thin Film Sensorics 28 
2.3.1 Advantages of Ultrathin Films for Sensorics 28 
2.3.2 Ultrathin Pyrosensors 30 
2.3.2.1 State of the Art 30 
2.3.2.2 Definitions and Measurements 31 
2.3.2.3 Rationale for Using Thin Organic Films for Pyroelectric Devices 35 
2.3.2.4 Pyroelectric Cells and Measuring Techniques 36 
2.3.2.5 Pyroelectricity of Organic Thin Films 43 
2.3.2.6 Polymer Thin Film Pyroelectricity 46 
2.3.2.7 Pyroelectric Measurements 47 
2.3.2.8 Materials and Experimental Set-Up 47 
2.3.2.9 Sample Preparation and Experimental Procedure 49 
2.3.2.10 Pyroelectric Response and Long-Term Stability 50 
2.3.2.11 Control of Pyroelectric Response 52 
2.3.3 Humidity LB Polyelectrolyte Sensors 54 
2.3.4 Commercial Application of LB Film Devices 58 
2.4 Molecular Electronic Devices 60 
2.4.1 Problems and Opportunities 60 
2.4.2 Optically Switchable Thin Films 62 
2.4.2.1 E-Z-Switching of Azo-Compounds 62 
2.4.3 Molecular Rectifier 73 
2.4.4 Electroluminescence of Organic Thin Films 77 
2.4.5 Ultrathin Films as Electron beam Resists 79 
2.5 Outlook 83 
List of Abbreviations 83 
References 85 
Chapter 3 
Polymers for Optical Fiber Sensors 
F. Baldini, S. Bracci 
3.1 Introduction 91 
3.2 The Optical Fiber Sensor 92 
3.2.1 The Optoelectronic System 92 
3.2.2 The Optical Link 93 
3.2.3 The Optode 93 
3.3 Polymers in Optical Fiber Chemical Sensors 95 
3.4 Polymer Functions 97 
3.4.1 Polymers as Solid Supports 97 
3.4.2 Polymers as Selective Elements 101 
3.4.3 Polymers as Chemical Transducers 103 
3.5 Conclusions 105 
List of Symbols and Abbreviations 106 
References 106 
Chapter 4 
Smart Ferroelectric Ceramic/Polymer Composite Sensors 
D.-K. Das-Gupta 
4.1 Introduction 109 
4.2 Basic Concepts 110 
4.2.1 Piezoelectricity 110 
4.2.2 Pyroelectricity 114 
4.2.3 Ferroelectric Ceramics 115 
4.2.4 Ferroelectric Polymers 116 
4.3 Ferroelectric Ceramic/Polymer Composites 118 
4.3.1 Connectivity 118 
4.3.2 03 Connectivity Composites and their Fabrication 120 
4.3.3 13 Connectivity Composite Fabrication 121 
4.3.4 33 Connectivity Composite Preparation 122 
4.3.5 Preparation of Composites with Mixed Connectivity (03 and 13) 122 
4.4 Poling Methods of Ceramic/Polymer Composites 123 
4.4.1 D.C. Poling 124 
4.4.2 A.C. Poling 125 
4.5 Piezoelectric Properties of Ceramic/Polymer Composites 127 
4.6 Pyroelectric Properties of Ceramic/Polymer Composites 
with 03 Connectivities 131 
4.7 Models of 03 and Mixed Connectivity Composites 133 
4.7.1 Yamada Model for 03 Composites 133 
4.7.2 Furukaura Model for 03 Composites 134 
4.7.3 Parallel and Series Connected Two-Dimensional Structure 135 
4.8 Applications of Ceramic/Polymer Composite Sensors 142 
4.8.1 Composite Transducers with 13 Connectivity 143 
4.8.2 Composite Transducers with 03 and Mixed Connectivity 143 
References 144 
Chapter 5 
Sensing Volatile Chemicals Using Conducting Polymer Arrays 
R. A. Bailey, K. C. Persaud 
5.1 Introduction 149 
5.1.1 Gas Sensor Technologies 152 
5.1.1.1 Metal Oxide Semiconductor (MOS) Sensors 152 
5.1.1.2 Quartz Crystal Microbalance (QCM) Sensors 152 
5.1.1.3 Surface Acoustic Wave (SAW) Sensors 153 
5.1.1.4 Amperometric Sensors 153 
5.1.1.5 Pellistor Sensors 153 
5.1.1.6 Metal-Substituted Phthalocyanine Sensors 153 
5.1.1.7 Organic Conducting Polymer (OCP) Gas Sensors 154 
5.1.1.8 Other Sensor Technologies 154 
5.1.1.9 Combination Gas Sensors 154 
5.2 Implementation of a Conducting Polymer Sensor Array 155 
5.2.1 Conducting Polymer Sensors 155 
5.2.1.1 Preparation of Polypyrrole 156 
5.2.1.1.1 Electrochemical Synthesis 157 
5.2.1.1.2 Chemical Synthesis 157 
5.2.1.2 Polymerisation Mechanism 158 
5.2.1.2.1 Factors Affecting the Polymerisation Process 159 
5.2.1.2.1.1 Electrochemical Conditions 159 
5.2.1.2.1.2 Counterion Effects 160 
5.2.1.2.1.3 Other Effects 160 
5.2.2 Structure of Polypyrrole 161 
5.2.3 Conductance Mechanism 162 
5.2.3.1 Classical Band Theory 162 
5.2.3.2 Conducting Polymer Mechanisms 163 
5.2.4 Composite Polymers 165 
5.3 Gas Sensing 166 
5.3.1 Gas Sampling System 167 
5.3.2 Data Acquisition Hardware 168 
5.3.3 Data Acquisition and Manipulation Software 169 
5.3.4 Pattern Recognition Techniques 170 
5.4 Linear Solvation Energy Relationships (LSER) and 
the Investigation of Gas Sensor Responses 170 
5.5 Conclusion 177 
References 178 
Chapter 6 
Molecular Machines Useful for the Design of Chemosensors 
S. Shinkai, M. Takeuchi, A. Ikeda 
6.1 Introduction 183 
6.2 Chromogenic Crown Ethers 184 
6.3 Photoresponsive Crown Actuators in Action for Ion 
and Molecule Recognition 186 
6.4 Cyclodextrins Modified as Molecule Sensors 190 
6.5 Calixarenes Modified as Ion and Molecule Sensors 193 
6.6 New Artificial Sugar Sensing Systems in which the Boronic 
Acid-Diol Interaction is Combined with Photoinduced 
Electron-Transfer (PET) 196 
6.7 Conclusion 205 
References 205 
Chapter 7 
Conducting Polymer Actuators: Properties and Modeling 
A. Mazzoldi, A. Della Santa, D. De Rossi 
7.1 Introduction 207 
7.2 Working Principles and Actuator Configurations 209 
7.3 Figures of Merit of a CP Actuator 211 
7.4 Actuators in the Literature 216 
7.5 Materials and Techniques for Fabrication 217 
7.5.1 Films 217 
7.5.1.1 Film Electrochemical Deposition 217 
7.5.1.2 Film Preparation by Casting 218 
7.5.2 Fibers 219 
7.5.3 All Polymer Actuators 219 
7.5.3.1 Dry PANi Fiber Actuator 219 
7.5.3.2 Dry PPyClO_4 Film Actuator 222 
7.6 Continuum Electromechanics of CP Actuators 223 
7.6.1 Introduction to the Continuum Model 223 
7.6.2 The Continuum Approach 224 
7.6.3 Configuration of Study 224 
7.6.4 Mechanical Equations 224 
7.6.5 Electrochemical Equations 227 
7.6.5.1 Relations Between the Charges and Equations for the Redox Reactions 227 
7.6.5.2 Motion Equations of Ionic Charges 228 
7.6.5.3 Relation Between Current and Potential in the Solid Matrix 229 
7.6.5.4 Continuity Equations 229 
7.6.5.5 Resolvability 230 
7.6.6 Resolution and Validation of the Model in the Passive Case 230 
7.6.6.1 Model Resolution 231 
7.6.6.2 Experimental Determination of the Parameters Considered 
in the Passive Case 232 
7.6.6.3 Passive Continuum Model Testing 234 
7.6.6.3.1 Empirical Corrections 236 
7.7 Lumped Parameter Description of a PC Actuator 237 
7.7.1 Model 237 
7.7.2 Parameters Estimation and Validation 239 
7.7.2.1 Passive Condition 239 
7.7.2.2 Active Condition 240 
7.8 Conclusions 243 
References 244 
Chapter 8 
Electrically Induced Strain in Polymer Gels Swollen 
with Non-Ionic Organic Solvents 
T. Hirai, M. Hirai 
8.1 Introduction 245 
8.2 Electrically Induced Strain in PVA-DMSO Gel 245 
8.2.1 Electrostrictive Motion of PVA-DMSO Gel 245 
8.2.2 Detailed Feature of the Electrically Induced Action 
of the PVA-DMSO Gel 247 
8.2.3 Comparison with PAAM-DMSO Gel 248 
8.3 Effect of Crosslinks on the Electrostrictive Strain 249 
8.3.1 Preparation Method of the DMSO Gel 249 
8.3.2 Effect of Solvent Content on the Performance of the Actuation 249 
8.4 Structural Change in PVA-DMSO Gel Induced by Electric Field 251 
8.4.1 Orientation of DMSO by Electric Field 251 
8.4.1.1 In PVA-DMSO Gel 251 
8.4.1.2 Comparison with PVC-DMSO Gel 252 
8.4.2 Electrically Induced Structure Change Observed 
by Small Angle X-Ray Scattering (SAXS) 252 
8.4.2.1 Scattering Functions 252 
8.4.2.2 Distance Distribution Functions 255 
8.4.2.3 Persistence Length and Correlation Length 255 
8.5 On the Mechanism of the Electrostrictive Action 
and Concluding Remarks (for Future Development) 256 
References 257 
Chapter 9 
Actuating Devices of Liquid-Crystalline Polymers 
R. Kishi 
9.1 Introduction 259 
9.2 Lyotropic Liquid-Crystalline Polymer Gels 260 
9.2.1 Poly(gamma-benzyl L-glutamate) Gels Having Cholesteric 
Liquid-Crystalline Order 260 
9.2.2 Poly(gamma-benzyl L-glutamate) Gels Having Nematic 
Liquid-Crystalline Order 263 
9.2.3 Optical Anisotropy of Poly(gamma-benzyl L-glutamate) Gels 
Having Cholesteric Liquid-Crystalline Order 265 
9.2.4 Poly(L-glutamic acid) Hydrogels Having Liquid-Crystalline Order 266 
9.3 Thermotropic Liquid-Crystalline Polymer Gels 268 
9.3.1 Electrical Deformation of Side-Chain Type 
Liquid-Crystalline Polymer Gels 268 
9.3.2 Electrorheological Properties of Thermotropic 
Liquid-Crystalline Materials 270 
9.4 Conclusion 271 
References 272 
Chapter 10 
Gel Actuators 
J. P. Gong, Y. Osada 
10.1 Introduction 273 
10.2 Shape Memory Gel 274 
10.3 Spontaneous Motion of Polymer Gels on Water 277 
10.4 Electrical Contraction and Tactile-Sensing System 280 
10.5 Gel Actuator Based on Molecular Assembly Reactions 283 
10.5.1 Gel Pendulum 284 
10.5.2 Gel Looper 287 
10.5.3 Gel-Eel 289 
10.6. Future Prospects 293 
References 294 
Chapter 11 
Electrochemomechanical Devices Based on Conducting Polymers 
T. F. Otero 
11.1 Introduction 295 
11.2 Approach Through Electrochemical Systems 297 
11.3 Artificial Molecular Muscles in the Literature 299 
11.4 Conducting Polymers: a Short Introduction 301 
11.5 Redox Processes in Conducting Polymers and Related Properties 302 
11.6 Artificial Muscles from Conducting Polymers 306 
11.7 Bilayer Devices 307 
11.8 Electrochemopositioning Devices 308 
11.9 The Working Muscle 309 
11.10 Triple Layer Devices 310 
11.11 Movement Rate Control 312 
11.12 Actuator and Sensor 313 
11.13 Lifetime and Degradation Processes 313 
11.14 Three-Dimensional Electrochemical Processes and 
Biological Mimicking 314 
11.14.1 Hydro-Organic Batteries 316 
11.14.2 Color Mimicking 317 
11.14.3 Nerve Interfaces 317 
11.14.4 Smart Membranes 318 
11.14.5 Mechanochemoelectrical Devices 318 
11.15 Theoretical Approaches 319 
11.16 Similarities with Natural Muscles 320 
11.17 The Future 321 
References 321 
Chapter 12 
Ion-Exchange Polymer-Metal Composites as Biomimetic Sensors and Actuators 
M. Shahinpoor 
12.1 Introduction 325 
12.2 Biomimetic Sensing Capability of IPMC 327 
12.2.1 General Considerations 327 
12.2.2 Theoretical Analysis 329 
12.2.3 Experimental Procedures, Results, and Discussion 331 
12.2.4 Dynamic Sensing 333 
12.2.5 Conclusions 334 
12.3 Biomimetic Actuation Properties of IPMCs 335 
12.3.1 General Considerations 335 
12.3.2 Development of Muscle Actuators 336 
12.3.3 Muscle Actuator for Robotic Applications 338 
12.3.4 Design of Linear and Platform Type Actuators 339 
12.3.5 Conclusions 340 
12.4 Large Amplitude Vibrational Response of IPMCs 342 
12.4.1 General Considerations 342 
12.4.2 Theoretical Model 342 
12.4.3 Experimental Observations 343 
12.4.4 Conclusions 346 
12.5 Load and Force Characterization of IPMCs 347 
12.5.1 General Considerations 347 
12.5.2 Results and Discussion 347 
12.5.3 Conclusions 350 
12.5.4 Force vs Displacement 350 
12.6 Electromechanical Modeling 351 
12.7 Summary 355 
References 356 
Chapter 13 
Motor Protein Mechanism Coupled with Hydrophobic Hydration/ 
Dehydration Cycle 
M. Suzuki, T. Kodama 
13.1 Introduction 361 
13.2 Dielectric Analysis of Hydrated Solute in Water 362 
13.3 Dielectric Properties of Motor Protein S1 364 
13.4 Hydrophobic Hydration and Accessible Surface Area of S1 365 
13.5 Dynamic Change of Hydrophobic Hydration 366 
13.6 Discussions 368 
References 369 
Chapter 14 
Actuating Systems in Biology 
J. F. V. Vincent 
14.1 Filamentous Actuators 371 
14.1.1 Actin and Myosin 371 
14.1.2 Microtubules and Kinesin/Dynein 372 
14.1.3 Flagellar Motors 373 
14.1.4 Mutable Collagenous Tissues 375 
14.1.5 Role of the Collagen Fibrils in Variable Stiffness 377 
14.2 Non-Fibrous Actuators 378 
14.2.1 The Spasmoneme 378 
14.2.2 Outer Hair Cells of the Inner Ear 379 
14.3 Pressure Systems 380 
14.3.1 Plants 380 
14.3.2 Nematocysts 381 
References 383 
Chapter 15 
Magnetic Field Sensitive Polymeric Actuators 
M. Zrnyi, D. Szab, L. Barsi 
15.1 Introduction 385 
15.2 Magnetostriction 385 
15.3 Ferrogel: a New Magnetostrictive Soft Material 386 
15.4 Magnetic Properties of Ferrogels 387 
15.5 Characterisation of Magnetic Field Distribution in One Dimension 390 
15.6 Elastic Properties of Ferrogels: Unidirectional Extension 392 
15.7 Giant Magnetostriction of Ferrogels as Seen by the Naked Eye 395 
15.8 Results of Unidirectional Magnetoelastic Measurements 396 
15.9 Ferrogels as Linear Magneto-Elastic Soft Actuators 399 
15.10 Interpretation of Noncontinuous Shape Transition 400 
15.11 Theoretical Basis for Design of Magnetic Gel Actuators 405 
15.12 Kinetics of the Shape Change 406 
15.13 Future Aspects 408 
References 408 
Subject Index 409 
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