Table of Contents
Preface v
1 Membrane and Membrane Separation Process 1
1.1 Size exclusion membranes 1
1.1.1 Microfiltration (MF) membrane 3
1.1.2 Ultrafiltration (UF) membrane 3
1.1.3 Nanofiltration (NF) membrane 4
1.2 Reverse osmosis (RO) membrane 4
1.3 Membrane structures 6
1.3.1 Symmetric and asymmetric membranes 6
1.3.2 Composite membrane 8
1.4 Polymer membranes 10
1.4.1 Cellulose and its derivatives 10
1.4.2 Polyamide (Nylon) 11
1.4.3 Polysulfone 12
1.4.4 Poly(vinyldene fluoride) (PVDF) 13
1.4.5 Polytetrafluroefhylene (PTFE) 14
1.4.6 Polypropylene (PP) 14
1.4.7 Polycarbonate (PC) 15
1.5 Inorganic (ceramic) membranes 15
1.5.1 Sintered ceramic membranes 15
1.5.2 Anodized alumina membrane 17
1.5.3 Molecular sieves (zeolites) 18
1.6 Membrane modules 19
1.6.1 Plate-and-frame membrane module 20
1.6.2 Spiral-wound membrane module 21
1.6.3 Tubular membrane module 21
1.6.4 Hollow fibre membrane module 22
1.7 Wide variety in membrane's driving force 25
1.7.1 Gas selective separation 26
1.7.2 Pervaporation membrane 27
1.7.3 Piezodialysis membrane 27
1.7.4 Dialysis membrane 28
1.7.5 Electrical dialysis membrane 29
1.7.6 Thermally driven membranes: Membrane distillation 30
1.8 Membrane's applications 31
1.8.1 Water treatment 32
1.8.2 Biomedical applications 35
2 Membrane Preparation 39
2.1 Phase separation method 39
2.2 Lithography-based membrane preparation techniques 41
2.2.1 Introduction of lithography 41
2.2.2 Photo masks and radiation sources in lithography 46
2.2.3 Lithography-based membrane preparation: Direct photo-etching 48
2.2.4 Micro-imprinting (or embossing) method 52
2.2.5 Combination of micro-printing and phase separation 55
2.2.6 Laser interference lithography 56
2.3 Non-woven membrane preparation 57
2.3.1 Traditional non-woven fabric 57
2.3.2 Non-woven polymer fabric by electrospinning 60
2.4 Other membrane preparation methods 65
2.4.1 Track-etching 65
2.4.2 Film stretching 67
2.4.3 Laser drilling 68
2.4.4 Template leaching 69
2.5 Example: Hollow fibre membrane preparation 69
3 Surface Modification of Polymers 71
3.1 Graft copolymerization 72
3.1.1 Radiation-induced graft copolymerization 73
3.1.2 Plasma-induced graft copolymerization 76
3.1.3 Oxidization-induced graft copolymerization 77
3.2 Plasma treatment 77
3.2.1 Plasma physics 78
3.2.2 Gas discharge plasma sources and equipments 81
3.2.3 Plasma-polymer interactions 87
3.2.4 Hydrophilicity and hydrophilicity manipulation 89
3.2.5 Plasma treatment of polymers with O-, N- or F-containing gases 89
3.2.6 Depth of plasma treatment and aging of polymer surfaces after plasma treatment 93
3.3 Chemical vapour deposition (CVD) 95
3.3.1 Introduction 95
3.3.2 Chemical versatility of CVD 96
3.3.3 PECVD 98
3.3.4 Polymer film formed by PECVD: Plasma polymer 100
4 Immobilization of Functional Molecules and its Chemistry 107
4.1 Nucleophiles and electrophiles 107
4.2 Hard and soft nucleophiles and electrophiles 112
4.3 Leaving group 113
4.4 Chemistry of functional groups 116
4.4.1 Carboxyl groups and carbodiimide chemistry 117
4.4.2 Hydroxyl groups 121
4.4.3 Thiol group (-SH) 125
4.4.4 Aldehyde groups 128
4.4.5 Isocynate group 129
4.4.6 Epoxide group 131
4.4.7 Cyanuric chloride (2,4,6-trichlorotriazine) 132
4.4.8 Amino groups (RNH2, R1,R2NH) 134
4.5 Modification agents 136
4.5.1 Modification agents for introduction of thiol group 136
4.5.2 Modification agents for introduction of carboxyl group 141
4.5.3 Modification agents for introduction of amino group 141
4.5.4 Modification agents for introduction of aldehyde group 143
4.6 Linking agents 144
4.6.1 Carbodiimides 144
4.6.2 Carbonyl diimidazole (CDI) 145
4.6.3 Homobifunctional NHS esters 147
4.6.4 Homobifunctional imidoesters 148
4.6.5 Homobifunctional sulfhydryl-reactive linking agents 150
4.6.6 Other homobifunctional linkers 150
4.6.7 Heterobifunctional linking reagents 150
4.7 Ligand immobilization on polymer surfaces 154
4.7.1 Polysaccharides 154
4.7.2 PTFE and PVDF 156
4.7.3 Nylon 158
4.7.4 Polysulfone and polyethersulfone 160
4.7.5 Poly(ethylene terephthalate) (PET) 160
5 Membrane Chromatography 165
5.1 Basics of chromatography 165
5.1.1 Gel filtration chromatography 168
5.1.2 Ion-exchange chromatography 170
5.1.3 Hydrophobic interaction chromatography 171
5.1.4 Reversed-phase chromatography 172
5.1.5 Affinity chromatography 172
5.1.6 Metal chelate affinity chromatography 173
5.2 IgG purification by affinity chromatography 175
5.2.1 IgG structure 175
5.2.2 Affinity ligands for IgG purification 177
5.3 Affinity membrane chromatography 180
5.4 Theory of affinity membrane chromatography 183
5.4.1 Band moving in chromatography system 184
5.4.2 Simulation of chromatography process: Continuous model 186
5.4.3 Simulation of chromatography process: Plate model 189
5.4.4 Simulation of affinity membrane chromatography process using plate model 191
5.5 Affinity membrane materials 195
5.5.1 Cellulose and its derivatives 196
5.5.2 Polyamide 198
5.5.3 Polysulphone 198
5.5.4 Polyethylene and polypropylene 199
5.5.5 Monoliths 200
5.6 Affinity membrane examples 201
5.6.1 ELIPSA™ 201
5.6.2 UltraBind™ affinity membrane (PALL) 203
5.6.3 Sartobind™ membranes 204
5.6.4 Vivapure™ Protein A Mini spin columns (Sartorious) 205
6 Membranes in Biosensors and Bioreactors 207
6.1 Membranes in biosensors 207
6.1.1 Amperometric biosensors 207
6.1.2 Gas permeable membranes in amperometric biosensors 211
6.1.3 Analyte permeable membrane in amperometric biosensors 213
6.1.4 Enzyme immobilized membranes in biosensors 215
6.1.5 Membranes in amperometric gas sensors 217
6.1.6 Ion-selective membrane for potentiometric biosensors 222
6.1.7 Membranes used in enzyme-ISFET biosensors 228
6.1.8 Electrospun nanofibre membrane for biosensors 235
6.2 Membrane-based enzyme bioreactors 237
6.3 Membrane bioreactors for waste water treatment 243
6.3.1 Introduction 243
6.3.2 Biological treatment rationale 245
6.3.3 Basic membrane systems of MBR 246
6.3.4 Example of MBR: Denitrification 249
Appendix A Phase Diagrams of Polymer Solutions and Application 255
A.1 Phase diagram of solvent polymer (SP) system 255
A.2 Derivation of phase diagram of the SP system with a generalized mathematical method 260
A.3 Phase diagram of nonsolvent solvent polymer (NSP) system 261
A.4 Application of phase diagram 264
Appendix B Plate Model of Chromatography 267
Bibliography 273
Index 285