ENCYCLOPEDIA OF SMART MATERIALS
CONTENTS CHAPTER 1? LIFE BIOINSPIRATION CHEMO BIOMIMESIS AND INTELLIGENT MATERIALS 1 1 1 INTRODUCTION 1 1 2 BASIC HYPOTHESES 1 1 3 BIOINSPIRATION BIOMIMESIS CHEMO BIOMIMESIS INTELLIGENT MATERIALS AND SYSTEMS 2 1 4 AVAILABLE REACTIVE MATERIALS 3 1 5 INTRINSIC CPS 4 1 5 1 AVAILABLE MATERIAL FAMILIES 5 1 6 BIOMIMETIC REACTIVE GELS 6 REFERENCES 8 CHAPTER 2? ELECTROCHEMICAL METHODS 12 2 1 INTRODUCTION 12 2 2 TWO ELECTRODE ELECTROCHEMICAL CELLS 12 2 3 THREE ELECTRODE ELECTROCHEMICAL CELLS 15 2 4 FOUR ELECTRODE ELECTROCHEMICAL CELLS 16 2 5 CYCLIC VOLTAMMETRY 17 2 5 1 VOLTAMMETRIC AND COULOVOLTAMMETRIC RESPONSES 19 2 5 2 ELECTROLYTE POTENTIAL WINDOW 20 2 6 SQUARE POTENTIAL STEPS CHRONOAMPEROMETRIC CHRONOCOULOMETRIC AND REACTION KINETIC RESPONSES 21 2 7 GALVANOSTATIC METHODOLOGIES CHRONOPOTENTIOMETRIC RESPONSES 23 2 8 ELECTROCHEMICAL CELLS AND METHODS USING SOLID STATE ELECTROLYTES 24 REFERENCES 25 CHAPTER 3? ELECTROSYNTHESIS OF CONDUCTING POLYMERS 26 3 1 INTRODUCTION 26 3 2 LINEAR POTENTIAL SWEEP MONOMER OXIDATION POTENTIAL 27 3 3 ELECTROPOLYMERIZATION BY CONSECUTIVE POTENTIAL SWEEPS 27 3 3 1 ELECTROPOLYMERIZATION AND POLYMER PASSIVATION DEGRADATION 30 3 4 ELECTROPOLYMERIZATION AT A CONSTANT POTENTIAL POTENTIOSTATIC 31 3 5 ELECTROPOLYMERIZATION BY CONSECUTIVE SQUARE POTENTIAL WAVES 33 3 6 ELECTROPOLYMERIZATION BY FLOW OF A CONSTANT CURRENT GALVANOSTATIC 34 3 7 TAFEL SLOPE MECHANISM USING CLEAN METAL ELECTRODES 35 3 8 ELECTROPOLYMERIZATION MECHANISM 35 3 9 ELECTROCHEMICAL AND GRAVIMETRIC METHODOLOGIES 37 3 10 GRAVIMETRIC EMPIRICAL ELECTROPOLYMERIZATION KINETICS 38 3 11 EMPIRICAL KINETICS FROM THE ELECTROPOLYMERIZATION CHARGE 40 3 12 ELECTROCHEMICAL POLYMERIZATION KINETICS TAFEL SLOPES FROM CLEAN METAL ELECTRODES 41 3 13 TAFEL SLOPES FROM POLYMER COATED ELECTRODES 42 3 14 ELECTROPOLYMERIZATION AND THE PROPERTIES OF THE ELECTROGENERATED FILMS 42 3 15 ANALYSIS OF THE POLYMERIZATION KINETICS 44 3 16 PARALLEL POLYMERIC DEGRADATION CROSS LINKING DURING SYNTHESIS 44 3 17 PARALLEL CHEMICAL POLYMERIZATION 46 3 18 PARALLEL ADSORPTION OF MACROIONS 47 3 19 SHIFT OF THE MOLECULAR INTERACTION FORCES ELECTRODISSOLUTION 48 3 20 INCORPORATION OF DIFFERENT MATERIAL NANOPARTICLES 49 3 21 POLYMERIZATION MECHANISM 50 3 22 GENERAL COMMENTS 50 3 23 SYNTHESIS OF NEW POLYMERIC COMPOUNDS BY IONIC SUBSTITUTION 52 3 24 ELECTROPOLYMERIZATION INITIATED BY ELECTROCHEMICAL REDUCTION 52 REFERENCES 53 CHAPTER 4? GEL MEMBRANE ELECTRODES ELECTROCHEMICAL REACTIONS 59 4 1 INTRODUCTION 59 4 1 1 INERT AND REACTIVE ELECTRODES 60 4 2 CONDUCTING POLYMERS AS ELECTROACTIVE ELECTRODES 60 4 3 ELECTROCHEMICAL REACTIONS 61 4 4 SOME CONSIDERATIONS RELATED TO CONDUCTING POLYMER REACTIONS 63 4 5 GIANT NON STOICHIOMETRY TRANSFER OF CONSECUTIVE ELECTRONS AND CONTINUOUS POLYMER ION COMPOSITION EVOLUTION 64 4 6 IONIC COMPOSITION VARIATION WITH STABLE PHYSICAL INTEGRITY 66 4 7 ELECTROCHEMICAL RESPONSES FROM DIFFERENT METHODOLOGIES 68 4 7 1 VOLTAMMETRIC RESPONSES 69 4 7 2 COULOVOLTAMMETRIC RESPONSES FULL ELECTROCHEMICAL REVERSIBILITY 70 4 7 3 CHRONOAMPEROMETRIC RESPONSES 72 4 7 4 CHRONOPOTENTIOMETRIC RESPONSES 73 4 8 DETECTING PARALLEL IRREVERSIBLE REACTIONS 73 4 8 1 PARALLEL IRREVERSIBLE REACTIONS FROM FILMS COATING METAL ELECTRODES 74 4 8 2 PARALLEL IRREVERSIBLE REACTIONS FROM SELF SUPPORTED POLYMERIC ELECTRODES 75 REFERENCES 77 CHAPTER 5? MEMBRANE COMPOSITION DEPENDENT ELECTROCHEMICAL PROPERTIES 81 5 1 INTRODUCTION 81 5 2 ELECTRONIC CONDUCTIVITY 81 5 3 VOLUME VARIATION 83 5 4 COLOR SHIFT 83 5 5 CHARGE STORAGE 86 5 6 IONIC STORAGE 87 5 7 TRANSVERSAL IONIC CONDUCTIVITY AND DIFFUSIVITY TUNING 87 5 8 MATERIAL POTENTIAL SHIFT 87 5 9 SURFACE PROPERTY CONTROL 88 5 10 ION DELIVERY 88 5 11 PACKED IONIC CONFORMATIONAL ENERGETIC STATES 88 5 12 CHEMO BIOMIMETIC FUNCTIONS 89 5 13 ICM ELECTRO CHEMO BIOMIMICRY 90 REFERENCES 90 CHAPTER 6? REACTION DRIVEN CONFORMATIONAL ALLOSTERIC AND STRUCTURAL CHANGES 92 6 1 INTRODUCTION 92 6 2 REVERSIBLE CHAIN MOLECULAR MOTORS 92 6 3 OXIDATION REDUCTION REACTIONS DRIVE MACROSCOPIC STRUCTURAL CHANGES 94 6 4 REACTION DRIVEN STRUCTURAL COMPONENTS 94 6 4 1 REACTION DRIVEN ANION EXCHANGES 95 6 4 2 REACTION DRIVEN CATION EXCHANGES 97 6 5 ERASING STRUCTURAL AND CHEMICAL MEMORIES STEADY STATE RESPONSES 99 6 6 OTHER ELECTROCHEMICAL RESPONSES REVEAL REACTION DRIVEN STRUCTURAL CHANGES 100 6 7 VOLTAMMETRIC RESPONSES 100 6 8 CHRONOAMPEROMETRIC RESPONSES 103 6 9 DIRECT VISUAL OBSERVATION OF THE OXIDATION RELAXATION NUCLEATION PROCESS 105 6 10 VISUAL TRACING OF THE GIANT NON STOICHIOMETRIC NATURE OF CONDUCTING POLYMERS 107 6 11 RELAXATION NUCLEATION STARTS AT THE POLYMER ELECTROLYTE INTERFACE 108 6 12 CHRONOPOTENTIOMETRIC RESPONSES 110 6 13 ION TRAPPING BY STRUCTURAL EFFECTS 110 6 13 1 ION TRAPPING DURING ELECTROPOLYMERIZATION 110 6 13 2 ANION TRAPPING BY REDUCTION COMPACTION DURING P DEDOPING 111 6 13 3 CATION TRAPPING BY OXIDATION COMPACTION DURING N DEDOPING OR P DOPING 111 6 13 4 LOW BAND GAP POLYMERS TRAP ANIONS DURING P DEDOPING AND CATIONS DURING N DEDOPING 111 6 14 ANALYTICAL EVIDENCES OF THE IONIC CONTENT IN DEEPLY REDUCED FILMS 113 6 15 ELECTRONIC CONDUCTIVITY OF DEEPLY REDUCED FILMS 114 6 16 HYDROGEN INHIBITION FROM AQUEOUS SOLUTIONS 115 6 17 IN SITU MONITORING OF REACTION DRIVEN DIMENSIONAL CHANGES 115 6 18 IN SITU MONITORING OF REACTION DRIVEN MASS VARIATIONS 116 6 19 INFLUENCE OF THE CHARGE BALANCING ION DIMENSIONS 116 6 20 SOLVENT INFLUENCE 117 6 21 OTHER REACTION DRIVEN CONFORMATIONAL ALLOSTERIC AND STRUCTURAL RESPONSES FROM DIFFERENT ARTIFICIAL AND BIOLOGICAL MATERIALS 118 6 22 PHYSICAL DRIVEN CONFORMATIONAL CHANGES 118 REFERENCES 119 CHAPTER 7? CONFORMATIONAL ALLOSTERIC AND STRUCTURAL CHEMISTRY THEORETICAL DESCRIPTION 124 7 1 INTRODUCTION 124 7 2 THE ESCR MODEL 127 7 2 1 CONFORMATIONAL RELAXATION NUCLEATION RELAXATION TIME CONFORMATIONAL ENERGY AND RELAXATION ENERGY 129 7 2 2 STRUCTURE AND CHEMICAL REACTIONS 130 7 2 3 STRUCTURAL CHEMICAL KINETIC SCK MODEL 131 7 2 4 STRUCTURAL ACTIVATION ENERGY 136 7 2 5 STRUCTURAL REACTION COEFFICIENT 138 7 2 6 STRUCTURAL REACTION ORDERS 139 7 2 7 THE SCK MODEL INCLUDES CHEMICAL KINETIC MODELS 139 7 3 STRUCTURAL CHRONOAMPEROMETRIC RESPONSES THEORETICAL SIMULATION 140 7 4 STRUCTURAL VOLTAMMETRIC RESPONSES THEORETICAL DESCRIPTION 142 7 5 STRUCTURAL COULOVOLTAMMETRIC RESPONSES THEORETICAL DESCRIPTION 145 7 6 STRUCTURAL CHRONOPOTENTIOMETRIC RESPONSES THEORETICAL DESCRIPTION 145 7 7 FINAL CONSIDERATIONS 148 REFERENCES 149 CHAPTER 8? ELECTRO CHEMO BIOMIMETIC DEVICES 152 8 1 INTRODUCTION 152 8 2 ARTIFICIAL MUSCLES 153 8 2 1 BILAYER AND TRI LAYER BENDING DEVICES 155 8 2 2 ELECTRO CHEMO DYNAMIC CHARACTERIZATION OF ARTIFICIAL MUSCLES 156