Materials science of membranes for gas and vapor separation

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Materials Science of Membranes for Gas and Vapor Separation is a one-stop reference for the latest advances in membrane-based separation and technology. Put together by an international team of contributors and academia, the book focuses on the advances in both theoretical and experimental materials science and engineering, as well as progress in membrane technology. Special attention is given to comparing polymer and inorganic/organic separation and other emerging applications such as sensors.

This book aims to give a balanced treatment of the subject area, allowing the reader an excellent overall perspective of new theoretical results that can be applied to advanced materials, as well as the separation of polymers. The contributions will provide a compact source of relevant and timely information and will be of interest to government, industrial and academic polymer chemists, chemical engineers and materials scientists, as well as an ideal introduction to students.

Author Notes

Dr Y.P. Yampolskii, Topchiev Institute of Petrochemical Synthesis, Moscow, Russia

Dr I. Pinnau , Membrane Technology and Research, Inc., Menlo Park, CA, USA

Professor B.D. Freeman , University of Texas at Austin, TX, USA

Scott Matteucci and Yuri Yampolskii and Benny D. Freeman and Ingo PinnauDoros N. TheodorouJoel R. FriedFerruccio Doghieri and Massimiliano Quinzi and David G. Rethwisch and Giulio C. SartiJohannes G. (Hans) Wijmans and Richard W. BakerYuri Yampolskii and Victor ShantarovichAlexander Alentiev and Yuri YampolskiiToshio Masuda and Kazukiyo NagaiTim C. Merkel and Ingo Pinnau and Rajeev Prabhakar and Benny D. FreemanKazuhiro Tanaka and Ken-Ichi OkamotoPeter H. PfrommGeorge R. GavalasHidetoshi KitaTadashi UragamiHidetoshi KitaYong Soo Kang and Jong Hak Kim and Jongok Won and Hoon Sik KimRichard D. Noble and Carl A. Koval

Contributors	p. xiii
Preface	p. xvii
1 Transport of Gases and Vapors in Glassy and Rubbery Polymers	p. 1
1.1 Background and Phenomenology	p. 1
1.2 Effects of Gas and Polymer Properties on Transport Coefficients	p. 7
1.2.1 Effect of Gas Properties on Solubility and Diffusivity	p. 7
1.2.2 Effect of Polymer Properties on Transport Parameters	p. 14
1.3 Effect of Pressure on Transport Parameters	p. 18
1.3.1 Sorption	p. 18
1.3.2 Diffusion	p. 22
1.3.3 Permeability	p. 22
1.3.4 Selectivity	p. 22
1.4 Effect of Temperature on Transport Parameters	p. 30
1.5 Structure/Property Relations	p. 31
1.5.1 Connector Groups	p. 35
1.5.2 CF[subscript 3] and Other Fluorinated Moieties as Side-chains	p. 36
1.5.3 Polar and Hydrogen Bonding Side-chains	p. 36
1.5.4 Para versus Meta Linkages	p. 37
1.5.5 Cis/Trans Configuration	p. 37
1.6 Conclusions	p. 38
References	p. 40
2 Principles of Molecular Simulation of Gas Transport in Polymers	p. 49
2.1 Introduction	p. 49
2.2 Generating Model Configurations for Amorphous Polymers	p. 50
2.2.1 Models and Force Fields	p. 50
2.2.2 Molecular Mechanics	p. 52
2.2.3 Molecular Dynamics	p. 52
2.2.4 Monte Carlo	p. 53
2.2.5 Coarse-graining Strategies	p. 54
2.2.6 Generating Glasses from Melts	p. 55
2.3 Validating Model Amorphous Polymer Configurations	p. 57
2.3.1 Thermodynamic Properties	p. 57
2.3.2 Molecular Packing	p. 58
2.3.3 Segmental Dynamics	p. 59
2.3.4 Accessible Volume and its Distribution	p. 61
2.4 Prediction of Sorption Equilibria	p. 64
2.4.1 Sorption Thermodynamics	p. 64
2.4.2 Calculations of Low-pressure Sorption Thermodynamics	p. 67
2.4.3 Calculations of High-pressure Sorption Thermodynamics	p. 68
2.4.4 Ways to Overcome the Insertion Problem	p. 70
2.5 Prediction of Diffusivity	p. 72
2.5.1 Statistical Mechanics of Diffusion	p. 72
2.5.2 Self-diffusivities from Equilibrium Molecular Dynamics	p. 73
2.5.3 Diffusivities from Nonequilibrium Molecular Dynamics	p. 74
2.5.4 Diffusion in Low-temperature Polymer Matrices as a Sequence of Infrequent Penetrant Jumps	p. 75
2.5.5 Gusev-Suter TST Method for Polymer Matrices Undergoing Isotropic 'Elastic' Motion	p. 77
2.5.6 Multidimensional TST Approach to Gas Diffusion in Glassy Polymers	p. 80
2.5.7 Anomalous Diffusion: Its Origins and Implications	p. 86
2.6 Conclusions and Outlook	p. 87
Acknowledgements	p. 89
References	p. 89
3 Molecular Simulation of Gas and Vapor Transport in Highly Permeable Polymers	p. 95
3.1 Fundamentals of Membrane Transport	p. 95
3.1.1 Solubility	p. 95
3.1.2 Diffusivity	p. 96
3.1.3 Permeability	p. 97
3.1.4 Free Volume	p. 99
3.1.5 d-Spacing	p. 101
3.1.6 Transport in Semicrystalline Polymers	p. 101
3.2 Computational Methods	p. 101
3.2.1 Solubility	p. 102
3.2.2 Diffusivity	p. 102
3.2.3 Free Volume	p. 104
3.2.4 d-Spacing	p. 105
3.2.5 Pair Correlation Functions	p. 105
3.2.6 Molecular Mobility	p. 105
3.2.7 Guidelines for Molecular Simulations	p. 105
3.3 Polymer Studies	p. 106
3.3.1 Polyetherimide	p. 107
3.3.2 Polysulfones	p. 107
3.3.3 Polycarbonates	p. 108
3.3.4 Poly(2,6-dimethyl-1,4-phenylene oxide)	p. 109
3.3.5 Polyimides	p. 110
3.3.6 Polyphosphazenes	p. 114
3.3.7 Main-chain Silicon-containing Polymers	p. 116
3.3.8 Poly[1-(trimethylsilyl)-1-propyne]	p. 120
3.3.9 Amorphous Teflon	p. 124
3.4 Conclusions	p. 126
Appendices: Primary Force Fields Used in the Simulation of Transport in Polymeric Systems	p. 126
Appendix 1 DREIDING	p. 126
Appendix 2 GROMOS	p. 126
Appendix 3 COMPASS	p. 127
References	p. 127
4 Predicting Gas Solubility in Membranes through Non-Equilibrium Thermodynamics for Glassy Polymers	p. 137
4.1 Introduction	p. 137
4.2 Background	p. 138
4.2.1 Pseudo-solubility Calculation	p. 140
4.2.2 Lattice Fluid Model (Sanchez and Lacombe)	p. 141
4.2.3 Tangent-Hard-sphere-Chain Equation of State	p. 142
4.2.4 Retrieving Parameters and Building Pseudo-Equilibrium Solubility Models	p. 143
4.3 Solubility Calculation and Comparison with Experimental Data	p. 144
4.3.1 Prediction of the Low-pressure Gas Solubility in Glassy Polymers	p. 144
4.3.2 Prediction of the Low-pressure Solubility Coefficient of Gases in Glassy Polymers	p. 148
4.3.3 Correlation of Low-pressure Solubility Coefficients in Glassy Polymers	p. 151
4.3.4 Correlation of High-pressure Gas Solubility in Glassy Polymers	p. 153
4.4 Discussion and Conclusions	p. 155
Acknowledgements	p. 157
References	p. 157
5 The Solution-Diffusion Model: A Unified Approach to Membrane Permeation	p. 159
5.1 Introduction	p. 159
5.2 The Solution-Diffusion Model	p. 159
5.3 One-component Transport in Hyperfiltration (Reverse Osmosis), Gas Separation and Pervaporation Membranes	p. 163
5.3.1 Hyperfiltration (Reverse Osmosis)	p. 163
5.3.2 Gas Separation	p. 166
5.3.3 Pervaporation	p. 167
5.4 A Unified View	p. 170
5.5 Multi-component Transport in Hyperfiltration (Reverse Osmosis), Gas Separation and Pervaporation Membranes	p. 173
5.5.1 Hyperfiltration (Reverse Osmosis)	p. 173
5.5.2 Gas Separation	p. 178
5.5.3 Pervaporation	p. 182
5.6 Conclusions and Future Directions	p. 187
References	p. 188
6 Positron Annihilation Lifetime Spectroscopy and Other Methods for Free Volume Evaluation in Polymers	p. 191
6.1 Introduction	p. 191
6.2 Free Volume: Definitions and Effects on the Transport Parameters	p. 192
6.3 Positron Annihilation Lifetime Spectroscopy	p. 193
6.4 [superscript 129]Xe NMR Study	p. 200
6.5 Inverse Gas Chromatography	p. 201
6.6 Other Probe Methods	p. 205
6.6.1 Photochromic Probes	p. 205
6.6.2 Electrochromic Probes	p. 205
6.7 Conclusions	p. 206
Appendix List of Polymers	p. 206
References	p. 207
7 Prediction of Gas Permeation Parameters of Polymers	p. 211
7.1 Introduction	p. 211
7.2 Group Contribution Methods	p. 215
7.3 Graph Theoretical Approach	p. 222
7.4 Artificial Neural Networks	p. 223
7.5 Computer Simulations	p. 224
7.6 Conclusions	p. 226
References	p. 227
8 Synthesis and Permeation Properties of Substituted Polyacetylenes for Gas Separation and Pervaporation	p. 231
8.1 Introduction	p. 231
8.2 Polymer Synthesis	p. 233
8.2.1 General Features of the Polymerization	p. 233
8.2.2 Poly[1-(trimethylsilyl)-1-propyne] and its Analogues	p. 234
8.2.3 Polydiarylacetylenes and their Derivatives	p. 236
8.2.4 Ring-substituted Polyphenylacetylenes	p. 238
8.3 Gas and Vapor Separation	p. 239
8.3.1 Gas/Gas Separation	p. 239
8.3.2 Vapor/Gas Separation	p. 241
8.3.3 Vapor/Vapor Separation	p. 243
8.4 Pervaporation	p. 244
8.4.1 Alcohol/Water Separation	p. 244
8.4.2 Organic Liquid/Water Separation	p. 245
8.4.3 Organic Liquid/Organic Liquid Separation	p. 246
8.5 Concluding Remarks	p. 246
References	p. 247
9 Gas and Vapor Transport Properties of Perfluoropolymers	p. 251
9.1 Introduction	p. 251
9.2 Amorphous Perfluoropolymers as Membrane Materials	p. 252
9.3 The Nature of Fluorocarbon/Hydrocarbon Interactions	p. 260
9.3.1 Differences in Ionization Potentials between Fluorocarbons and Hydrocarbons	p. 261
9.3.2 Non-central Force Fields	p. 263
9.4 Conclusions	p. 266
References	p. 267
10 Structure and Transport Properties of Polyimides as Materials for Gas and Vapor Membrane Separation	p. 271
10.1 Introduction	p. 271
10.2 Fundamentals	p. 273
10.2.1 Packing Density of Polyimides	p. 273
10.2.2 Transport Properties	p. 274
10.2.3 Diffusion and Solubility Coefficients of Gases	p. 275
10.3 Effect of Morphology	p. 276
10.4 Factors Controlling Transport Properties	p. 277
10.4.1 Factors Controlling Diffusion Coefficient	p. 277
10.4.2 Factors Controlling Solubility Coefficient	p. 280
10.5 Structure-Property Relationship	p. 281
10.5.1 Effect of Structures of Acid Dianhydrides	p. 281
10.5.2 Effect of Structures of Diamines	p. 282
10.5.3 Separation Performance for Particular Systems	p. 283
10.5.4 A Group Contribution Method for Polyimides	p. 285
10.5.5 Enhancement of Solubility Selectivity for CO[subscript 2]/N[subscript 2] Separation	p. 285
10.5.6 Enhancement of Diffusivity Selectivity for H[subscript 2]/CH[subscript 4] Separation	p. 287
10.5.7 Water Vapor Permeation	p. 287
10.6 Conclusions	p. 288
References	p. 288
11 The Impact of Physical Aging of Amorphous Glassy Polymers on Gas Separation Membranes	p. 293
11.1 Introduction	p. 293
11.2 Scope	p. 294
11.3 Observations on Integral-Asymmetric Membranes	p. 294
11.4 Physical Aging of Glassy Polymers	p. 295
11.4.1 The Experimental Challenge Posed by Glassy Polymers	p. 295
11.4.2 The Glassy State in Amorphous Polymers	p. 295
11.4.3 Aging Mechanisms and Models	p. 296
11.5 The Thickness-dependence of Aging in Glassy Polymers	p. 297
11.5.1 Influence of the Thickness on T[subscript g], Density, and Free Volume	p. 297
11.5.2 A Phenomenological Model for Thickness-Dependent Aging	p. 298
11.5.3 Influence of the Thickness on Time-dependent Properties of Thin Polymer Films far below the T[subscript g]	p. 298
11.5.4 Special Case: Aging of Poly(trimethylsilyl propyne)	p. 302
11.6 Implications of Thickness-dependent Aging for Practical Membrane Gas Separations	p. 304
11.7 Concluding Remarks	p. 304
References	p. 304
12 Zeolite Membranes for Gas and Liquid Separations	p. 307
12.1 Introduction	p. 307
12.2 Membrane Preparation	p. 309
12.2.1 General Issues	p. 309
12.2.2 MFI Membrane Preparation	p. 310
12.2.3 Zeolite A Membrane Preparation	p. 315
12.2.4 Zeolite Y Membrane Preparation	p. 316
12.3 Characterization	p. 316
12.3.1 General on Techniques and Results	p. 316
12.3.2 Membrane Defects	p. 320
12.4 Permeation Measurements	p. 321
12.4.1 Measurement Techniques	p. 321
12.4.2 Survey of Permeation Results	p. 323
12.5 Theory and Modeling of Transport in Zeolite Membranes	p. 331
12.6 Concluding Remarks	p. 332
Acknowledgements	p. 333
References	p. 333
13 Gas and Vapor Separation Membranes Based on Carbon Membranes	p. 337
13.1 Introduction	p. 337
13.2 Preparation and Characterization of Carbon Membranes	p. 338
13.2.1 Self-supported Carbon Membranes	p. 338
13.2.2 Supported Carbon Membranes	p. 345
13.3 Gas Transport and Separation	p. 349
13.4 Vapor Permeation and Pervaporation	p. 351
13.5 Conclusions	p. 352
References	p. 353
14 Polymer Membranes for Separation of Organic Liquid Mixtures	p. 355
14.1 Introduction	p. 355
14.2 Structural Design of Polymer Membranes	p. 355
14.2.1 Chemical Design of Membrane Materials	p. 355
14.2.2 Physical Construction of Polymer Membranes	p. 356
14.3 Separation Mechanism	p. 356
14.3.1 Pervaporation	p. 356
14.3.2 Evapomeation	p. 358
14.3.3 Temperature-difference Controlled Evapomeation	p. 359
14.4 Separation of Organic Liquid Mixtures	p. 359
14.4.1 Alcohol/Water Separation	p. 359
14.4.2 Hydrocarbon/Water Separation	p. 362
14.4.3 Organic/Organic Separation	p. 364
14.4.4 Benzene/Cyclohexane Separation	p. 365
14.5 Conclusions	p. 368
References	p. 369
15 Zeolite Membranes for Pervaporation and Vapor Permeation	p. 373
15.1 Introduction	p. 373
15.2 Zeolite Membranes for Water/Organic Liquid Separation	p. 374
15.2.1 Hydrophilic Membranes	p. 374
15.2.2 Organophilic Membranes	p. 379
15.3 Zeolite Membranes for Organic/Organic Separation	p. 381
15.3.1 Alcohol/Ether Separation	p. 381
15.3.2 Aromatic/Non-Aromatic Separation	p. 383
15.3.3 Xylene Isomer Separation	p. 384
15.4 Integrated Systems Involving Pervaporation or Vapor Permeation by Zeolite Membranes	p. 385
15.5 Manufacture of Zeolite Membranes for Pervaporation and Vapor Separation	p. 386
15.6 Conclusions	p. 387
References	p. 388
16 Solid-State Facilitated Transport Membranes for Separation of Olefins/Paraffins and Oxygen/Nitrogen	p. 391
16.1 Introduction	p. 391
16.2 Carrier Properties and Transport Mechanism	p. 392
16.2.1 Carrier Properties	p. 392
16.2.2 Transport Mechanism	p. 398
16.3 Mathematical Models	p. 400
16.3.1 Dual-sorption Model	p. 400
16.3.2 Effective Diffusion Coefficient Model	p. 401
16.3.3 Limited Mobility of Chained Carriers Model	p. 401
16.3.4 Concentration Fluctuation Model	p. 402
16.3.5 Hopping Model versus Concentration Fluctuation Model	p. 403
16.4 Separation Performance of Olefins and Oxygen	p. 403
16.4.1 Olefins/Paraffins Separation	p. 404
16.4.2 Oxygen/Nitrogen Separation	p. 405
16.5 Membrane Stability	p. 405
16.6 Conclusions	p. 407
References	p. 408
17 Review of Facilitated Transport Membranes	p. 411
17.1 Introduction	p. 411
17.2 Experimental Methods	p. 412
17.3 Modeling	p. 413
17.4 Membrane Configurations	p. 416
17.5 Hybrid Processes	p. 418
17.6 Additional Driving Forces	p. 418
17.7 Methods for Implementation of Active Transport	p. 419
17.8 Novel Liquid Phases - Ionic Liquids	p. 421
17.9 Novel Liquid Phases - Electrohydrodynamic Fluids	p. 422
17.10 Incorporation of the Complexing Agent into the Membrane	p. 423
17.11 Unsaturated Hydrocarbons	p. 423
17.11.1 Scope of Research	p. 423
17.11.2 Mechanistic Studies	p. 424
17.11.3 Membrane Morphology	p. 424
17.11.4 Olefin-Ag(I) Complexation	p. 424
17.11.5 Effect of Water on Performance	p. 425
17.11.6 Other Complexing Agents	p. 426
17.12 Gas Separations	p. 426
17.12.1 Oxygen/Nitrogen Separations	p. 426
17.12.2 Carbon Dioxide Separations	p. 427
17.13 Organic Substances	p. 427
17.14 Biological Complexing Agents	p. 428
17.15 Concluding Remarks	p. 428
References	p. 428
Index	p. 437

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