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Full Description
An accurate and up-to-date exploration of molecular and ionic transport phenomena through polymeric membranes
In Molecule and Ion Transport through Polymer Membranes, distinguished researcher Yong Soo Kang delivers an authoritative and organized resource about polymeric membrane technology. The book introduces the fundamentals of the transport phenomena of neutral molecules and ions as well as the underlying common principles between the two.
The author establishes a foundation for designing new polymeric materials using basic principles, like Fick's law, and to introduce a variety of fundamental theories and concepts about polymer structure and permeation properties. Readers will also find:
A thorough introduction to the underlying principles and experimental techniques necessary to study molecular and ionic transport processes
Comprehensive explorations of the separation and transportation of small molecules and ions by membranes
Practical discussions of the transport properties of neutral molecules and ions
Complete treatments of fundamental principles and theories relevant to mass transport through polymeric membranes
Perfect for polymer chemists, process engineers, electrochemists, membrane scientists, and materials scientists, Molecule and Ion Transport through Polymer Membranes will also benefit mechanical and chemical engineers.
Contents
Preface xi
Acknowledgement xiii
1 Overview of Molecule and Ion Transport Through Polymer Membranes 1
1.1 Molecule Transport 2
1.2 Ion Transport 3
1.3 Similarities and Differences Between Molecule and Ion Transport 4
1.3.1 Free Volume Theory 4
1.3.2 Facilitated Transport in the Solid State 5
1.3.3 Diffusion and Migration 7
1.3.4 Transport Parameters and Electroneutrality 7
1.4 Overview of Molecule and Ion Transport Through Polymer Membranes 8
1.4.1 Fundamentals on Polymeric Materials 9
1.4.2 Part 1: Molecule Transport Through Polymer Membranes 9
1.4.3 Part 2: Ion Transport Through Polymer Membranes 10
References 11
2 Introduction to Polymeric Materials 13
2.1 Interactions of Polymer with Solvent and Polymer Solution 13
2.1.1 Flory-Huggins Lattice Theory 14
2.1.2 Solubility Parameter Approach 15
2.1.3 Limitations and Modifications of Flory-Huggins Theory 17
2.2 Phase Diagram and Phase Separation 18
2.2.1 Phase Diagram 19
2.2.2 Phase Separation 19
2.3 Rubbery and Glassy Polymers 20
2.3.1 Rubbery vs Glassy Polymers 21
2.3.2 Glass Transition Temperature 21
2.3.3 Theories for Glass Transition Temperatures 22
2.4 Nonequilibrium Features of Glassy Polymers 24
2.4.1 Nonequilibrium Features of Glassy Polymers and Physical Aging 24
2.4.2 Characterization of Sub-glass Transitions by Dynamic Mechanical
Analysis 25
2.5 Free Volume Theory and Applications 26
2.5.1 Free Volume Theory 27
2.5.2 Applications of Free Volume Theory 28
2.5.3 Measurement of Free Volume 30
2.6 Crystalline Polymers 31
2.6.1 Crystal Structures 31
2.6.2 Crystallization Kinetics and the Degree of Crystallinity 32
2.7 Polymer Blends 33
2.8 Viscoelastic and Mechanical Properties 34
2.8.1 Viscoelastic Properties 34
2.8.2 Stress-Strain Behavior 35
References 36
Part I Molecule Transport Through Polymer Membranes 39
3 Molecule Transport Through Polymer Membranes 41
3.1 Fick's Law and Solution-diffusion Mechanism 41
3.2 Sorption and Permeation Features in a Slab 43
3.2.1 Transient Sorption 44
3.2.2 Transient Permeation 45
3.3 Diffusion Through Polymers 46
3.3.1 Constant Diffusion Coefficient 46
3.3.2 Concentration-dependent Diffusion Coefficient 47
3.3.3 Temperature-dependent Diffusion and Theories for Activation Energy 48
3.3.4 Diffusion in Crystalline Polymers 50
3.4 Statistical View of Diffusion Coefficient 51
3.5 Free Volume Theory for Diffusion 52
3.5.1 Free Volume in Polymers 53
3.5.2 Theory of Cohen and Turnbull 54
3.5.3 Theory of Fujita 56
3.5.4 Theory of Miyamoto and Shibayama, and Vrentas and Duda 58
3.5.5 Temperature- and Concentration-dependent Diffusion Coefficients 58
3.5.6 Advantages and Limitations of Free Volume Theory 59
3.5.7 Measurement and Estimation of Free Volume and d -spacing 61
3.6 Sorption in Polymers 63
3.6.1 Thermodynamic View of Sorption 64
3.6.2 Sorption of Permanent Gases in Polymers 64
3.6.3 Sorption of Condensable Gas and Vapor in Rubbery Polymers 66
3.6.4 Sorption of Condensable Gas and Vapor in Glassy Polymers: Dual Sorption Model 67
3.6.5 Temperature-dependent Sorption 68
3.6.6 Sorption in Crystalline Polymers 69
3.7 Permeation Through Polymers 70
3.7.1 Structure-Properties Relationships for Gas Permeation 71
3.7.2 Gas Permeation in Polymers with Extremely Stiff Chains and High Free Volume 73
3.7.3 Effects of Free Volume or d-spacing on Permeation 76
3.7.4 Temperature-dependent Permeation 78
3.7.5 Gas Permeation Through Crystalline Polymers 79
3.8 Mathematical Models for Transient Sorption and Permeation Through Glassy Polymers and Composite Membranes 79
3.8.1 Transient Sorption and Permeation for a Glassy Slab 80
3.8.2 Transient Sorption for a Glassy Sphere 81
3.8.3 Time-dependent Surface Concentration 82
3.8.4 Transient Sorption for a Composite Film 83
3.9 Transient Sorption of Organic Vapor in Polymers 85
3.9.1 Transient Sorption of Organic Vapor in Rubbery Polymers 85
3.9.2 Transient Sorption of Organic Vapor in Glassy Polymers 86
3.9.3 Transient Sorption of Organic Vapor in Composite Membranes 87
3.10 Mass Transport Overview: Fickian vs non-Fickian Behavior 88
References 89
4 Facilitated Transport Phenomena in the Solid State 93
4.1 Facilitated Transport in the Liquid State and the Solid State 94
4.2 Mathematical Models for Facilitated Transport in the Solid State 96
4.2.1 Dual-mode Transport Model 97
4.2.2 Effective Diffusion Coefficient Model 98
4.2.3 Limited Chain Mobility Model 99
4.2.4 Concentration Fluctuation Model 101
4.3 Concentration Fluctuation Model vs Direct Hopping Models 105
4.4 Facilitated Oxygen Transport 106
4.4.1 Reversible Oxygen Solubility 107
4.4.2 Kinetics of Reversible Interactions 108
4.4.3 Facilitated Oxygen Transport 108
4.5 Facilitated Olefin Transport 109
4.5.1 Metallic Ion Carriers 109
4.5.2 Surface-activated Metallic Nanoparticular Carriers 115
4.6 Facilitated CO2 Transport in Solid and Quasi-solid States 121
4.6.1 Interactions of CO2 with Lewis Bases and Acids in Aqueous Solution 122
4.6.2 Polymer Membranes with Lewis Bases 128
4.6.3 Polymer Electrolyte Membranes with Lewis Acids 131
4.6.4 Polymer Membranes with Ionic Liquids 134
4.6.5 Surface-activated Metallic Nanoparticle 138
4.7 Challenges and Prospects 139
References 140
5 Selective Transport Membranes 145
5.1 Definitions of Permeability and Selectivity 146
5.2 Overview for Separation Performance of Gas Mixtures 147
5.3 Theoretical Basis for Relationship Between Permeability and Selectivity (Upper-bound Curves) 148
5.4 Polymeric Structure-Properties Relationship 151
5.4.1 Polymers with Flexible Chains and High Free Volume 152
5.4.2 Ductile and Tough Glassy Polymers 153
5.4.3 Polymers with Extremely Stiff Chains and High Free Volume 155
5.4.4 Emerging Polymer Materials 160
5.5 Time-dependent Separation Performance: Physical Aging and Plasticization Effects in Glassy Polymers 163
5.5.1 Physical Aging and Permeability Changes 163
5.5.2 Physical Aging and Plasticization with Highly Sobule Diluents 164
5.6 Facilitated Transport Membranes in the Solid and Quasi-solid States 166
5.7 Oxygen Separation with Facilitated Transport Membranes 167
5.8 Olefin Separation with Facilitated Transport Membranes 168
5.8.1 Polymer Electrolyte Membranes Containing Metallic Ion Carriers 169
5.8.2 Surface-activated Metallic Nanoparticle Carriers 173
5.9 Carbon Dioxide Separation with Facilitated Transport Membranes 175
5.9.1 Polymer Membranes with Lewis Bases 176
5.9.2 Polymer Membranes with Lewis Acids 180
5.9.3 Polymer Membranes with Ionic Liquids (ILs) 183
5.9.4 Bicontinuous Structures Including Ion Exchange Membranes 189
5.9.5 Effects of Water in Quasi-solid Membranes 191
References 192
6 Measurement of Molecule Transport Properties 199
6.1 Definitions of Diffusion Coefficient, Solubility Coefficient, and Permeability 200
6.2 Permeation and Sorption Features in a Slab Membrane 202
6.3 Permeation Method for a Slab Membrane: Manometric and Time-lag Methods 202
6.3.1 Theoretical Backgrounds 202
6.3.2 Experimental Methods for Permeation 203
6.4 Sorption Method for a Slab Membrane: Gravimetric Methods 205
6.4.1 Theoretical Backgrounds 205
6.4.2 Experimental Methods for Transient Sorption 206
6.4.3 Experimental Methods for Equilibrium Sorption 208
6.5 Concentration-dependent Diffusion Coefficient 209
6.6 Variable Surface Concentration 209
6.7 Sorption in a Sphere 210
6.8 Pulsed Field Gradient (PFG)-NMR for Diffusion Coefficient 211
References 212
7 Applications of Selective Transport Membranes 213
7.1 Structure and Transport Through Composite Membranes 214
7.2 Mathematical Model for Composite Membranes: Resistance Model 216
7.3 Fabrication of Composite Membranes 219
7.3.1 Thermally Induced Phase Separation 220
7.3.2 Nonsolvent-induced Phase Separation 221
7.4 Structures and Mass Transport in Modules 222
7.4.1 Structures of Representative Membrane Modules 222
7.4.2 Membrane Modules for Gas Separation 223
7.5 Applications of Gas Transport Membranes 223
7.5.1 Hydrogen Separation 224
7.5.2 Oxygen/Nitrogen Separation 225
7.5.3 Carbon Dioxide Separation 226
7.5.4 Olefin/Paraffin Separation 229
7.6 Conclusions and Future Directions 230
7.6.1 Established Processes 230
7.6.2 Developing Processes 230
7.6.3 Emerging Processes 230
References 231
Part II Ion Transport Through Polymer Membranes 233
8 Basic Electrochemistry for Ion Transport 235
8.1 Electrochemical Devices and Key Terminologies 235
8.1.1 Reduction vs Oxidation 235
8.1.2 Galvanic Cells vs Electrolytic Cells 236
8.1.3 Cathode vs Anode and Positive Electrode vs Negative Electrode 237
8.1.4 Charge Transport vs Charge Transfer 237
8.1.5 Electric Potential vs Electric Energy 238
8.2 Electric Potential 239
8.2.1 Electrode Potential 239
8.2.2 Standard Electrode Potential 240
8.2.3 Concentration-dependent Electrical Potential: Nernst Equation 240
8.3 Electrochemical Redox Reactions and Charge Transfer Kinetics 242
8.3.1 Electrochemical Redox Reaction Kinetics 242
8.3.2 Current-Voltage Relationship: The Butler-Volmer Equation 244
8.3.3 Tafel Plot 246
8.4 Interfacial Charge Transfer Through Electric Double Layer 247
8.4.1 Electric Double Layer 247
8.4.2 Charge Transfer Through Electric Double Layer 249
8.5 Transport of Charged Species and Electric Current 250
8.5.1 Electrochemical Potential 251
8.5.2 Transport of Charged Species: Diffusion, Migration, and Convection 251
8.5.3 Electric Current Density 253
8.5.4 Ion Conductivity, Transport, and Transference Numbers 254
References 255
9 Polymer Electrolytes 257
9.1 Definitions of Ion Conductivity, Mobility, and Transport Numbers 257
9.2 Formation of Polymer Electrolyte to Generate Charge Carriers 258
9.2.1 Thermodynamics for Formation of Polymer Electrolytes 258
9.2.2 Generation of Free Charge Carriers 263
9.3 Polymeric Chain Mobility and Glass Transition Temperature 265
9.4 Mechanism of Ionic Transport 268
9.4.1 Free Volume Model 269
9.4.2 Conformational Entropy Model 271
9.4.3 Dynamic Bond Percolation Model 272
9.4.4 Anderson and Stuart Model 273
9.5 Ionic Conduction and Transport Number Through Polymer Electrolytes 274
9.5.1 Solid Polymer Electrolytes Based on PEO 275
9.5.2 Emerging Polymeric Solvents 276
9.5.3 Polymer-in-Salts: Novel Approach 276
9.5.4 Nanocomposites 280
9.5.5 Transport Number 280
9.6 Temperature Dependence of Ionic Transport 281
9.6.1 Vogel-Tamman-Fulcher Equation 282
9.6.2 Williams-Landal-Ferry Equation and Master Curves 283
9.7 Interfacial Charge Transfer Between SPE and Electrode 284
9.8 Prospects of Polymer Electrolytes 285
References 285
10 Ion-exchange Membranes 289
10.1 Definitions of Ion Conductivity, Transport Number, and Permselectivity 289
10.2 Ion Transport Through Water and Heterocycles 291
10.2.1 H+ and OH- Ion Transport Mechanisms 291
10.2.2 Proton Conduction Through Heterocycles 292
10.3 Structures of Ion Exchange Membranes: CEM, AEM, and BPM 293
10.3.1 Chemical Structure of Cation Exchange Membranes 294
10.3.2 Chemical Structure of Anion Exchange Membranes 295
10.3.3 Morphology of Ion Exchange Membranes 301
10.3.4 Water Absorption and Structural Evolution 302
10.4 Electric Field Generation at Bipolar Membrane Junction 304
10.4.1 Abrupt Bipolar Junction Model 305
10.4.2 Neutral Layer at Bipolar Junction Model 307
10.5 Transport Models of Ions in Ion Exchange Membranes 308
10.5.1 Facilitated Ion Transport Model Through Ion Channels 309
10.5.2 Condensed Counterion Model 311
10.6 Ion Transport Through Ion Exchange Membranes 314
10.6.1 Nernst-Planck Equation for Ion Transport 314
10.6.2 Proton Conductivity and Diffusion Coefficient in Cation Exchange Membranes 315
10.6.3 Hydroxide Ion Conductivity in Anion Exchange Membranes 316
10.6.4 Concentration Polarization 318
10.7 Selective Transport Through Ion Exchange Membranes: Permselectivity 321
10.7.1 Donnan Effects for Permselectivity of Counterion over Co-ion 321
10.7.2 Permselectivity of the Same Charged Ions 324
10.7.3 Transport of Water and Gas 325
10.8 Interrelationship Between Conductivity and Selectivity 329
References 331
11 Measurement of Ion Transport Properties 335
11.1 Experimental Techniques 335
11.2 Direct Current Techniques 335
11.2.1 Linear Sweep Voltammetry (LSV) 336
11.2.2 Cyclic Voltammetry (CV) 336
11.2.3 Potentiostatic Intermittent Titration Technique (PITT) 341
11.3 Alternating Current Techniques 342
11.3.1 Nyquist and Bode Plots 342
11.3.2 Electrochemical Impedance Spectroscopy (EIS) 347
11.4 Transport Number Measurements 350
References 350
12 Applications of Ion Transport Membranes 353
12.1 Polymer Electrolyte for Secondary Batteries 353
12.1.1 Basic Chemistry and Configuration of Secondary Batteries 353
12.1.2 Issues of Liquid Electrolytes 355
12.1.3 Advantages and Issues of Polymer Electrolytes 355
12.1.4 Challenges for Interfaces with Polymer Electrolytes 355
12.2 Polymer Electrolytes for Sensitized Solar Cells 357
12.2.1 Basic Chemistry and Configuration of Sensitized Solar Cells 358
12.2.2 Issues of Liquid Electrolytes 360
12.2.3 Advantages and Issues of Polymer Electrolytes 360
12.2.4 Oligomer Approach 361
12.2.5 Future and Challenges of Polymer Electrolytes for Sensitized Solar Cells 362
12.3 Ion Exchange Membranes for Fuel Cells 363
12.3.1 Basic Chemistry and Configuration of Fuel Cells 364
12.3.2 Roles and Requirements of Ion Exchange Membranes 365
12.3.3 Performance of PEMFCs and AEMFCs 366
12.3.4 Future and Challenges of IEMs 368
12.4 Applications of Ion Exchange Membranes for Electrochemical Water Splitting 368
12.4.1 Basic Electrochemistry and Configuration of Water-Splitting Electrolyzers 369
12.4.2 Roles and Requirements of Ion Exchange Membranes 371
12.4.3 Water Splitting with CEMs and AEMs 371
12.4.4 Water Splitting with Bipolar Membranes 373
12.4.5 Mathematical Models for Electric Field-Enhanced Water Dissociation 374
12.4.6 Future and Challenges for Electrochemical Water Splitting 377
References 378
Index 383
