60 Years of The Loeb Sourirajan Membrane Principles New Materials Modelling Characterization and Applications Hui Hsin Tseng Full Chapter

60 Years of the Loeb-Sourirajan
Membrane: Principles, New Materials,

Modelling, Characterization, and
Applications Hui-Hsin Tseng
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60 Years of the
Loeb-Sourirajan Membrane
60 Years of the Loeb-
Sourirajan Membrane
Principles, New Materials, Modelling,
Characterization, and Applications
Edited by
Hui-Hsin Tseng
Department of Environmental Engineering, National Chung Hsing University,
Taichung, Taiwan
Woei Jye Lau

Advanced Membrane Technology Research Centre (AMTEC), School of Chemical
and Energy Engineering, Universiti Teknologi Malaysia, Skudai, Malaysia
Mohammad A. Al-Ghouti
Environmental Science Program, Department of Biological and
Environmental Sciences, College of Arts and Sciences, Qatar University, Doha, Qatar
Liang An
Department of Mechanical Engineering, The Hong Kong
Polytechnic University, Hong Kong, P.R. China
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Contents
List of contributors ................................................................................. xvii

About the editors .................................................................................... xxv
Preface .................................................................................................. xxvii
Chapter 1 Ionic liquid based membranes for gas separation .................... 1

Eiji Kamio
1.1 Introduction.........................................................................................1
1.1.1 Ionic liquids ............................................................................ 2
1.1.2 Gas permeability of room-temperature ionic
liquid based membranes ..................................................... 4
1.2 Ionic liquid based CO2 separation membranes .............................8
1.2.1 Supported ionic liquid membranes .................................... 10
1.2.2 Pressure-resistant ionic liquid based membranes......... 11
1.3 CO2-reactive ionic liquid based facilitated-transport
membranes.......................................................................................17
1.3.1 Design concepts of CO2-reactive ionic liquids and
CO2 permeation mechanisms of CO2-reactive ionic
liquid based supported ionic liquid membranes ............. 17
1.3.2 Amine-functionalized ionic liquid based supported
ionic liquid membranes ....................................................... 18
1.3.3 Amino acid ionic liquid based supported ionic liquid
membranes .......................................................................... 19
1.3.4 Supported ionic liquid membranes containing aprotic
heterocyclic anion based ionic liquids............................. 21
1.3.5 Supported ionic liquid membranes containing ionic
liquids with carboxylate anions........................................... 22
1.4 Ion gel membranes containing task-specific ionic liquids ...........23
1.4.1 Ion gel membranes containing amino acid ionic
liquids and aprotic heterocyclic anion based ionic
liquids.................................................................................... 23
1.4.2 Ion gel membranes with epoxy amine gel networks ........ 25
1.5 Conclusion and remarks .................................................................26
References ................................................................................................26
v
vi Contents
Chapter 2 Zwitterionic polymers in biofouling and inorganic fouling

mechanisms .................................................................................. 33
Harout Arabaghian, Meng Wang, John Ordonez and
Debora F. Rodrigues
2.1 Introduction.......................................................................................33
2.2 Zwitterionic membrane fabrication and characterization ............37
2.2.1 Grafting processes for membrane modification ............... 37
2.2.2 Membrane modification by in situ modification ................ 42
2.3 Zwitterionic polymers and inorganic fouling .................................44
2.3.1 Zwitterionic polymers and ionic interactions..................... 45
2.3.2 Mineral scaling on ZI-modified membranes ..................... 46
2.4 Zwitterionic polymers and organic fouling ....................................47
2.4.1 The Mechanisms of zwitterionic polymers’ resistance
to organic fouling ................................................................. 48
2.4.2 The environmental conditions and organic foulants
that influence zwitterionic polymers .................................. 51
2.5 Zwitterionic polymers and biofouling .............................................53
2.5.1 Zwitterionic polymers and their interaction with
prokaryotic cells................................................................... 56
2.5.2 Zwitterionic polymers and their interaction with
eukaryotic cells .................................................................... 60
2.6 Conclusions and further remarks ..................................................63
Acknowledgement .....................................................................................65
References ................................................................................................65
Chapter 3 Recent advances in 3D printed membranes for water

applications.................................................................................... 71
Wae Zin Tan, Chai Hoon Koo, Woei Jye Lau, Woon Chan Chong
and Jing Yuen Tey
3.1 Introduction.......................................................................................71
3.2 3D printing technologies and classification ...................................73
3.2.1 Directed energy deposition ................................................. 74
3.2.2 Material jetting ..................................................................... 74
3.2.3 Sheet lamination .................................................................. 76
3.2.4 Binder jetting........................................................................ 76
3.2.5 Material extrusion ................................................................ 76
3.2.6 Powder bed fusion ............................................................... 77
3.2.7 Vat Photopolymerization...................................................... 77
3.2.8 Advantages and limitations of 3D printing methods ......... 78
3.2.9 Role and trend of 3D printing in membrane technology
for water applications.......................................................... 78
3.3 Applications of 3D printing in membrane technology...................80
3.3.1 Membrane fabrication via direct 3D printing..................... 81
3.3.2 Membrane surface modification via coating aided by
3D printing ............................................................................ 83
3.4 Conclusion and future perspectives ...............................................94
References ................................................................................................94
Contents vii
Chapter 4 A 15-year review of novel monomers for thin-film composite

membrane fabrication for water applications ............................ 97
John Ogbe Origomisan, Ying Siew Khoo, Woei Jye Lau,
Ahmad Fauzi Ismail and Adewale Adewuyi
4.1 Introduction.......................................................................................97
4.2 Commercial thin-film composite membranes ............................100
4.3 Novel amine monomers ................................................................101
4.3.1 Monomers bearing only NH2.......................................... 101
4.3.2 Monomers Bearing NH2/ OH and OH/ SO3............. 108
4.3.3 Monomers bearing multiple—hydroxyl groups ............... 110
4.3.4 Monomers for improved chlorine stability....................... 114
4.4 Novel acyl chloride monomers .....................................................115
4.4.1 Monomers with single/dual COCl ..................................... 118
4.4.2 Monomers with three COCls ............................................. 119
4.4.3 Monomers with Multiple COCls ........................................ 122
4.5 Comparison of novel thin-film composite membranes with
commercial membranes ...............................................................123
4.6 Conclusion ......................................................................................125
References ..............................................................................................126
Chapter 5 Recent advances in high-performance membranes for

vanadium redox flow battery...................................................... 131
Jiaye Ye, Jun Su, Huiyun Li and Lidong Sun
5.1 Introduction.....................................................................................131
5.1.1 The development of redox flow batteries ........................ 131
5.1.2 The essential role of membrane in a vanadium
redox flow battery .............................................................. 135
5.2 Inorganic modification ...................................................................136
5.2.1 Zero-dimensional nanoparticles....................................... 136
5.2.2 One-dimensional nanowires/nanotubes........................... 140
5.2.3 Two-dimensional nanosheets/nanoplates ....................... 143
5.3 Organic modification ......................................................................145
5.3.1 Covalent modification ........................................................ 145
5.3.2 Noncovalent modification .................................................. 146
5.4 Summary and outlook....................................................................148
References ..............................................................................................148
Chapter 6 Membranes for vanadium-air redox flow batteries................. 155

Xingyi Shi, Yanding Bi, Oladapo Christopher Esan and
Liang An
6.1 Introduction.....................................................................................155
6.2 General description........................................................................158
6.2.1 Working principles ............................................................. 158
6.2.2 Functional requirements of membranes ......................... 158
viii Contents
6.3 Membrane classifications..............................................................159

6.3.1 Commercial Nafion membranes ...................................... 159
6.3.2 Other membranes.............................................................. 160
6.4 Mechanisms and influences of species crossover ......................164
6.4.1 Oxygen permeation ............................................................ 164
6.4.2 Vanadium ion crossover .................................................... 166
6.4.3 Water transport.................................................................. 168
6.5 Performance-enhancing strategies for membranes ..................169
6.6 Summary.........................................................................................171
Acknowledgement ...................................................................................172
References ..............................................................................................172
Chapter 7 Carbon membrane for the application in gas separation:

recent development and prospects ........................................... 177
Yu-Ting Lin, Ming-Yen Wey and Hui-Hsin Tseng
7.1 Introduction.....................................................................................177
7.2 Designs of carbon membrane.......................................................180
7.2.1 Geometrical classifications ............................................... 180
7.2.2 Precursor selection for carbon membrane ..................... 182
7.2.3 Preparation of polymeric membrane ............................... 185
7.2.4 Pyrolysis procedure ........................................................... 188
7.2.5 Methods for tuning the pore dimension........................... 190
7.2.6 Module construction .......................................................... 193
7.3 Gas transport mechanism .............................................................195
7.4 Microstructure characterization ...................................................198
7.4.1 Raman................................................................................. 198
7.4.2 X-ray photoelectron spectroscopy .................................... 198
7.4.3 X-ray diffraction ................................................................. 199
7.4.4 Focused ion beam and transmission electron
microscopy.......................................................................... 200
7.5 Overall performance review for each gas pair ............................200
7.5.1 Hydrogen purification ........................................................ 200
7.5.2 Carbon sequestration ........................................................ 203
7.5.3 Air separation ..................................................................... 205
7.5.4 Natural gas sweetening..................................................... 205
7.6 Conclusion and outlook .................................................................208
Acknowledgment .....................................................................................208
References ..............................................................................................208
Chapter 8 Metal-organic framework membranes for gas separation

and pervaporation ....................................................................... 215
Dun-Yen Kang, Han-Lun Hung, Hsin-Yu Tsai, Jun-Yu Lai and
Ting-Hsiang Hung
8.1 Introduction.....................................................................................215
8.2 Fabrication of pure metal-organic framework membranes ......216
8.3 Metal-organic framework membranes for gas separations ......220
Contents ix
8.4 Computational efforts on metal-organic framework

membranes for gas separations...................................................227
8.5 Metal-organic framework membranes for pervaporation..........230
8.6 Conclusions and outlook ...............................................................232
References ..............................................................................................233
Chapter 9 Advanced ceramic membrane design for gas separation

and energy application ............................................................... 239
Tao Li, Mohamad Fairus Rabuni, Unalome Wetwatana Hartley
and Kang Li
9.1 Introduction.....................................................................................239
9.1.1 Micro-structured ceramic membranes............................ 240
9.1.2 Phase inversion assisted fabrication.............................. 242
9.1.3 Micro-channel formation and micro-structure
tailoring............................................................................... 243
9.2 Oxygen-permeable membrane and membrane reactor.............245
9.2.1 Oxygen transport in high-temperature ion
conductors .......................................................................... 245
9.2.2 Design of high-performance oxygen permeation
membrane .......................................................................... 247
9.2.3 Catalytic reactor based on oxygen-permeable
membrane .......................................................................... 253
9.3 Ceramic membrane in energy applications.................................254
9.3.1 Solid oxide fuel cell............................................................ 255
9.3.2 Coextrusion of functional membrane for
high-performance micro-tubular-solid oxide
fuel cells ............................................................................. 257
9.3.3 New micro-monolithic solid oxide fuel cell and
utilization of waste methane ............................................. 258
9.4 Conclusion ......................................................................................263
References ..............................................................................................264
Chapter 10 Recent advances in lithium-ion battery separators with

enhanced safety ........................................................................ 269
Weiqiang Lv and Xingyi Zhang
10.1 Introduction ............................................................................... 269
10.2 Self-shutdown separators........................................................ 271
10.3 Mechanically strong separators .............................................. 273
10.3.1 Increasing the tensile strength of separators.......... 274
10.3.2 Increasing the puncture strength of separators...... 278
10.4 Nonflammable separators ....................................................... 280
10.4.1 Ceramic-coated fibrous separators .......................... 284
10.4.2 Separators with flame-retardant additives .............. 286
10.5 All-solid-state electrolytes....................................................... 289
10.5.1 Solid polymer electrolytes ......................................... 289
x Contents
10.5.2 Inorganic all-solid-state electrolytes........................ 292

10.5.3 Composite organic inorganic solid electrolytes ..... 295
10.6 Future perspectives .................................................................. 297
References ........................................................................................... 298
Chapter 11 Silicon-based subnanoporous membranes with amorphous

structures .................................................................................. 305
Toshinori Tsuru
11.1 Introduction ............................................................................... 305
11.2 Development of subnanoporous membranes......................... 306
11.2.1 Organosilica membranes ........................................... 306
11.2.2 Silicon carbide based membranes .......................... 309
11.2.3 Plasma-enhanced chemical vapor deposition
membranes ................................................................. 309
11.3 Applications of membrane for gas phase separation............ 311
11.3.1 Application of silicon oxide based membranes
for gas separation....................................................... 311
11.3.2 Application of silicon-based nonoxide membranes
for gas separation....................................................... 314
11.3.3 Application of membranes for high-temperature
water vapor recovery.................................................. 314
11.4 Applications of membranes for solvent separation ............... 317
11.4.1 Evaluation of the separation energy of solvent
mixture ........................................................................ 317
11.4.2 Development and application of organic solvent
nanofiltration membranes ......................................... 319
11.4.3 Development and application of membranes for
organic solvent reverse osmosis............................... 321
11.5 Application to pervaporation .................................................... 322
11.5.1 Pervaporation dehydration using organosilica
membranes ................................................................. 323
11.5.2 Pervaporation of organic solvent mixtures .............. 324
11.6 Conclusion ................................................................................. 325
References ........................................................................................... 325
Chapter 12 Ultrafiltration mixed matrix membranes: metal organic

frameworks as emerging enhancers ...................................... 329
Mariam Ouda, Yazan Ibrahim, Hanaa Hegab, Fawzi Banat and
Shadi W. Hasan
12.1 Introduction ............................................................................... 329
12.2 Microenhancers and nanoenhancers ...................................... 331
12.3 Antifouling and antibacterial properties ................................. 334
12.4 Dye rejection.............................................................................. 339
12.5 Other applications..................................................................... 341
12.6 Conclusions and future outlook............................................... 344
References ........................................................................................... 345
Contents xi
Chapter 13 Zwitterion-modified membranes for water reclamation ...... 349

Gansheng Liu, Christine Matindi, Mengyang Hu, Xianhui Li,
Xiaohua Ma and Jianxin Li
13.1 Introduction ............................................................................... 349
13.2 Classification of zwitterionic polymers ................................... 351
13.2.1 Polybetaines ................................................................ 351
13.2.2 Polyampholytes........................................................... 355
13.3 Antifouling mechanisms of zwitterionic units in
membranes ............................................................................... 357
13.3.1 Classification of membrane foulants ........................ 357
13.3.2 Establishment of a hydration layer on the
membrane surface ..................................................... 358
13.3.3 Steric hindrance effect ............................................... 359
13.4 Preparation of zwitterion-modified membranes.................... 360
13.4.1 Modification by blending of zwitterionic
polymers...................................................................... 360
13.4.2 Modification by grafting.............................................. 363
13.4.3 Modification by surface coating................................. 366
13.4.4 Modification by surface quaternization ..................... 367
13.5 Applications of zwitterion-modified polymer
membranes ............................................................................... 368
13.5.1 Treatment of natural organic matter in water......... 368
13.5.2 Oily wastewater treatment......................................... 370
13.5.3 Textile wastewater treatment.................................... 374
13.5.4 Desalination................................................................. 375
13.6 Conclusion and prospects ........................................................ 377
Acknowledgments................................................................................. 377
References ........................................................................................... 377
Chapter 14 Modelling of spiral-wound membrane for gas separation:

current developments and future direction............................ 391
Abdul Aiman Abdul Latif, Kok Keong Lau and
Serene Sow Mun Lock
14.1 Introduction ............................................................................... 391
14.2 Construction and flow configuration of spiral-wound
membrane ................................................................................. 394
14.3 Modelling strategies ................................................................. 394
14.3.1 One-dimensional model ............................................. 396
14.3.2 Two-dimensional model............................................. 399
14.3.3 Three-dimensional model.......................................... 402
14.3.4 Summary of the mathematical models for
spiral-wound membrane............................................ 405
14.4 Challenges and future direction in modelling of
spiral-wound membrane in gas separation ........................... 408
14.4.1 Multicomponent separation ....................................... 408
xii Contents
14.4.2 Effect of pressure drop in feed and permeate

channel ........................................................................ 408
14.4.3 Effect of heat transfer within the module ................ 409
14.5 Conclusion ................................................................................. 410
References ........................................................................................... 410
Chapter 15 Modelling flow and mass transfer inside spacer-filled

channels for reverse osmosis membrane modules .............. 413
Yie Kai Chong, Yong Yeow Liang, Woei Jye Lau and
Gustavo Adolfo Fimbres Weihs
15.1 Introduction ............................................................................... 413
15.2 One-dimensional model ........................................................... 416
15.3 Two-dimensional model ........................................................... 418
15.4 Three-dimensional model ........................................................ 422
15.5 Conclusion ................................................................................. 429
Acknowledgment .................................................................................. 430
References ........................................................................................... 430
Chapter 16 Transport model-based prediction of polymeric

membrane filtration for water treatment ............................... 433
Krishnasri V. Kurada and Sirshendu De
16.1 Introduction ............................................................................... 433
16.2 Transport phenomena-based models ..................................... 436
16.2.1 Osmotic pressure-based models .............................. 436
16.3 Gel layer controlled mechanism............................................ 449
16.3.1 Transient one-dimensional gel layer controlling
model coupled with film theory................................. 449
16.3.2 Transient one-dimensional gel layer controlling
model coupled with a pore flow transport ............... 452
16.3.3 Modelling of mixed matrix membranes.................... 454
16.4 Conclusion ................................................................................. 459
References ........................................................................................... 460
Chapter 17 Molecular modelling and simulation of membrane

formation ................................................................................... 463
Zhen Wang, Sher Ling Lee, Tse-Chiang Huang,
Geng-Sheng Lin, Tomohisa Yoshioka and Kuo-Lun Tung
17.1 Molecular modelling and simulation....................................... 463
17.1.1 Introduction ................................................................. 463
17.1.2 Types of simulation methods..................................... 464
17.1.3 Section conclusions .................................................... 468
17.2 Modelling and simulations of membrane formation ............. 468
17.2.1 Phase separation ........................................................ 469
17.2.2 Dry casting .................................................................. 476
Contents xiii
17.2.3 Interfacial polymerization .......................................... 476

17.3 Modelling and simulation on hollow-fiber membrane .......... 479
17.3.1 Physical mass transfer model................................... 479
17.3.2 Dissipative particle dynamics .................................... 481
17.3.3 Finite element method ............................................... 482
17.4 Simulation and modelling in membrane design .................... 482
17.4.1 Graphene and two-dimensional carbon material .... 482
17.4.2 Zeolite imidazolate framework and
metal-organic membranes ........................................ 485
17.5 Future trends in molecular simulations of membrane
formation ................................................................................... 489
References ........................................................................................... 491
Chapter 18 Advanced characterization of membrane surface fouling .... 499

Kang Xiao, Yirong Xu, Xuyang Cao, Hao Xu and Yufang Li
18.1 Introduction ............................................................................... 499
18.2 Modelling of surface fouling .................................................... 500
18.2.1 Filtration laws ............................................................. 500
18.2.2 Compression of surface foulant layer....................... 502
18.2.3 Maturation and retardation of surface
foulant layer ................................................................ 503
18.2.4 Concentration polarization boundary layer .............. 503
18.3 Online characterization of surface fouling ............................. 504
18.3.1 Direct observation....................................................... 504
18.3.2 Optical coherence tomography.................................. 505
18.3.3 Attenuated total reflection Fourier transform
infrared spectroscopy................................................. 506
18.3.4 Raman spectroscopy .................................................. 506
18.3.5 Fluorescence spectroscopy ....................................... 507
18.3.6 Electrochemical impedance spectroscopy ............... 509
18.3.7 Quartz crystal microbalance with dissipation .......... 510
18.3.8 Surface plasmon resonance ...................................... 510
18.3.9 Light sheet fluorescence microscopy ....................... 511
18.4 Offline characterization of surface fouling ............................. 511
18.4.1 Microscopic methods ................................................. 511
18.4.2 Spectroscopic methods .............................................. 513
18.4.3 Other methods ............................................................ 519
18.4.4 Further data mining via statistical analysis ............. 521
18.5 Characterization of extracts from the surface foulant layer 521
18.5.1 Extraction of surface foulants ................................... 522
18.5.2 Chemical composition ................................................ 522
18.5.3 Physicochemical properties....................................... 522
18.5.4 Spectroscopic properties ........................................... 523
18.5.5 Chromatography ......................................................... 524
18.5.6 Biological properties .................................................. 525
18.6 Concluding remarks ................................................................. 526
References ........................................................................................... 527
xiv Contents
Chapter 19 Reverse osmosis membrane fouling and its physical,

chemical, and biological characterization .............................. 533
Mohammad Yousaf Ashfaq and Mohammad A. Al-Ghouti
19.1 Introduction ............................................................................... 533
19.2 Types of membrane fouling ..................................................... 534
19.2.1 Biofouling .................................................................... 535
19.2.2 Inorganic fouling/scaling............................................ 538
19.2.3 Organic fouling............................................................ 541
19.2.4 Colloidal/particulate fouling ...................................... 541
19.3 Membrane fouling characterization ........................................ 542
19.3.1 Microscopic techniques.............................................. 544
19.3.2 Spectroscopic and analytical techniques.................. 553
19.4 Conclusions ............................................................................... 565
Acknowledgment .................................................................................. 566
References ........................................................................................... 566
Chapter 20 Current status of ion exchange membranes for

electrodialysis/reverse electrodialysis and membrane
capacitive deionization/capacitive mixing ............................... 575
Nalan Kabay, Enver Güler, Katarzyna Smolinska-Kempisty
and Marek Bryjak
20.1 Ion exchange membranes in electrodialysis and
membrane capacitive deionization systems for water
demineralization ....................................................................... 575
20.1.1 Introduction ................................................................. 575
20.1.2 Electrodialysis ............................................................. 576
20.1.3 Membrane capacitive deionization ............................ 583
20.2 Ion exchange membranes for harvesting salinity gradient
energy ........................................................................................ 586
20.2.1 Introduction ................................................................. 586
20.2.2 Reverse electrodialysis .............................................. 587
20.2.3 Capacitive mixing........................................................ 592
20.3 Conclusion and future perspectives ........................................ 594
Acknowledgments................................................................................. 594
References ........................................................................................... 595
Chapter 21 Reverse osmosis membrane scaling during brackish

groundwater desalination......................................................... 603
Kai-Ge Lu, Haiou Huang and Mengya Li
21.1 Introduction ............................................................................... 603
21.2 Established theories for membrane-scaling formation ........ 604
21.2.1 Scaling thermodynamics............................................ 604
21.2.2 Scaling kinetics ........................................................... 605
21.3 Membrane scaling in brackish groundwater desalination .... 607
21.3.1 Brackish groundwater quality ................................... 607
Contents xv
21.3.2 Scaling types and morphology................................... 608

21.3.3 Effects of water quality on mineral scaling.............. 610
21.3.4 Relationships between membrane scaling and
permeate flux.............................................................. 612
21.4 Control strategies for membrane scaling .............................. 613
21.4.1 Feedwater pretreatment ............................................ 613
21.4.2 Antiscalants................................................................. 613
21.4.3 Operation mode of reverse osmosis system............ 615
21.4.4 Scaling-resistant reverse osmosis membrane ........ 616
21.5 Future challenges for mineral-scaling control ...................... 618
References ........................................................................................... 620
Chapter 22 Ceramic membrane in a solid oxide fuel cell based gas

sensor ........................................................................................ 627
Sutida Marthosa and Montri Luengchavanon
22.1 Introduction ............................................................................... 627
22.2 Research progress on ceramic membrane............................ 631
22.3 Issues in developing a micro-solid oxide fuel cell
methane sensor ........................................................................ 634
22.4 High temperature O-ring in a fuel cell testing station .......... 636
22.4.1 Current situation......................................................... 636
22.4.2 O-ring characteristics ................................................ 636
22.4.3 O-ring performance and thermally resistive
filler.............................................................................. 638
22.5 Micro-solid oxide fuel cell methane sensor ........................... 639
22.5.1 Current situation......................................................... 639
22.5.2 Sensor development overview ................................... 640
22.5.3 Design and character of the sensor.......................... 640
22.5.4 Sensor development................................................... 642
22.6 Conclusion ................................................................................. 646
Acknowledgment .................................................................................. 647
References ............................................................................................ 647
INDEX ...................................................................................................... 651

List of contributors
Abdul Aiman Abdul Latif

Department of Chemical Engineering, CO2 Research Center (CO2RES), Universiti
Teknologi PETRONAS, Bandar Seri Iskandar, Malaysia
Adewale Adewuyi
Department of Chemical Sciences, Faculty of Chemical Sciences, Redeemer's University,
Ede, Nigeria
Mohammad A. Al-Ghouti
Environmental Science Program, Department of Biological and Environmental Sciences,
College of Arts and Sciences, Qatar University, Doha, Qatar
Liang An
Department of Mechanical Engineering, The Hong Kong Polytechnic University, Hung
Hom, Kowloon, Hong Kong Special Administrative Region, P.R. China
Harout Arabaghian
Department of Biology and Biochemistry, University of Houston, Houston, TX,
United States
Mohammad Yousaf Ashfaq
Environmental Science Program, Department of Biological and Environmental Sciences,
College of Arts and Sciences, Qatar University, Doha, Qatar
Fawzi Banat
Department of Chemical Engineering, Center for Membranes and Advanced Water
Technology (CMAT), Khalifa University of Science and Technology, Abu Dhabi, United Arab
Emirates; Department of Chemical Engineering, Khalifa University of Science and
Technology, Abu Dhabi, United Arab Emirates
Yanding Bi
Marek Bryjak
Faculty of Chemistry, Wroclaw University of Science and Technology, Wroclaw, Poland
Xuyang Cao
College of Resources and Environment, University of Chinese Academy of Sciences,
Beijing, P.R. China xvii
xviii List of contributors
Woon Chan Chong

Lee Kong Chian Faculty of Engineering and Science, Universiti Tunku Abdul Rahman,
Kajang, Malaysia
Yie Kai Chong

College of Engineering, Universiti Malaysia Pahang, Lebuhraya Tun Razak, Gambang,
Kuantan, Pahang, Malaysia
Sirshendu De
Department of Chemical Engineering, Indian Institute of Technology Kharagpur,
Kharagpur, India
Oladapo Christopher Esan
Department of Mechanical Engineering, The Hong Kong Polytechnic University,
Hung Hom, Kowloon, Hong Kong Special Administrative Region, P.R. China
Gustavo Adolfo Fimbres Weihs
The University of Sydney, School of Chemical and Biomolecular Engineering, NSW, Australia
Enver Güler
Department of Chemical Engineering, Atılım University, Ankara, Turkey
Unalome Wetwatana Hartley
Chemical Process Engineering, The Sirindhorn International Thai-German Graduate School
of Engineering, King Mongkut's University of Technology North Bangkok, Bangkok, Thailand
Shadi W. Hasan
Hanaa Hegab
Mengyang Hu
State Key Laboratory of Separation Membranes and Membrane Processes, School of
Materials Science and Engineering, Tiangong University, Tianjin, P. R. China
Haiou Huang
School of Environment, Beijing Normal University, Beijing, P.R. China; Department of
Environmental Health and Engineering, The John Hopkins University, Baltimore, MD,
United States
Tse-Chiang Huang
Department of Chemical Engineering, National Taiwan University, Taipei, Taiwan, ROC;
Advanced Research Center for Green Materials Science and Technology (ARC-GMST),
National Taiwan University, Taipei, Taiwan, ROC
List of contributors xix
Han-Lun Hung
Department of Chemical Engineering, National Taiwan University, Taipei, Taiwan
Ting-Hsiang Hung
Yazan Ibrahim
Ahmad Fauzi Ismail
Advanced Membrane Technology Research Centre (AMTEC), School of Chemical and
Energy Engineering, Universiti Teknologi Malaysia, Skudai, Malaysia
Nalan Kabay
Department of Chemical Engineering, Ege University, Izmir Bornova, Turkey
Eiji Kamio
Center for Environmental Management, Kobe University, Nada-ku, Kobe, Japan; Department
of Chemical Science and Engineering, Kobe University, Nada-ku, Kobe, Japan; Research
Center for Membrane and Film Technology, Kobe University, Nada-ku, Kobe, Japan
Dun-Yen Kang
Ying Siew Khoo
Chai Hoon Koo
Kajang, Malaysia
Krishnasri V. Kurada
Department of Chemical Engineering GMR Institute of Technology, Rajam, India
Jun-Yu Lai
Kok Keong Lau
Woei Jye Lau
Sher Ling Lee

xx List of contributors
Huiyun Li
Center for Automotive Electronics, Shenzhen Institute of Advanced Technology, Chinese
Academy of Sciences, Shenzhen, P.R. China
Jianxin Li
Kang Li
Department of Chemical Engineering, Imperial College London, London, United Kingdom
Mengya Li
School of Environment, Beijing Normal University, Beijing, P.R. China
Tao Li
Jiangsu Provincial Key Laboratory of Solar Energy Science and Technology/Energy
Storage Joint Research Center, School of Energy and Environment, Southeast University,
Nanjing, P.R. China; Department of Chemical Engineering, Imperial College London,
London, United Kingdom
Xianhui Li
Key Laboratory for City Cluster Environmental Safety and Green Development of the
Ministry of Education, Institute of Environmental and Ecological Engineering, Guangdong
University of Technology, Guangzhou, P. R. China
Yufang Li
School of Environment, Tsinghua University, Beijing, P.R. China
Yong Yeow Liang
College of Engineering, Universiti Malaysia Pahang, Lebuhraya Tun Razak, Gambang,
Kuantan, Pahang, Malaysia
Geng-Sheng Lin
Yu-Ting Lin
Department of Environmental Engineering, National Chung Hsing University, Taichung,
Taiwan
Gansheng Liu
Materials Science and Engineering, Tiangong University, Tianjin, P. R. China; School of
Textile Science and Engineering, Tiangong University, Tianjin, P. R. China
Serene Sow Mun Lock
Kai-Ge Lu
College of Resources and Environment, Henan Agricultural University, Zhengzhou,
P.R. China
List of contributors xxi
Montri Luengchavanon
Wind Energy and Energy Storage Systems Centre (WEESYC), Faculty of Environmental
Management, Prince of Songkla University, Songkhla, Thailand; Center of Excellence in
Metal and Materials Engineering (CEMME), Prince of Songkla University, Hat Yai, Thailand
Weiqiang Lv
Yangtze Delta Region Institute (Huzhou) & School of Physics, University of Electronic
Science and Technology of China, Huzhou, P.R. China
Xiaohua Ma
Sutida Marthosa
Center of Excellence in Membrane Science and Technology, Faculty of Science and
Industrial Technology, Prince of Songkla University, Surat Thani Campus, Surat Thani,
Thailand
Christine Matindi
John Ordonez
Department of Civil and Environmental Engineering, University of Houston, Houston, TX,
United States
John Ogbe Origomisan
Energy Engineering, Universiti Teknologi Malaysia, Skudai, Malaysia; Department of
Chemical Sciences, Faculty of Chemical Sciences, Redeemer's University, Ede, Nigeria
Mariam Ouda
Mohamad Fairus Rabuni

Department of Chemical Engineering, Imperial College London, London, United Kingdom;
Department of Chemical Engineering, Universiti Malaya, Kuala Lumpur, Malaysia
Debora F. Rodrigues
United States
Xingyi Shi
Katarzyna Smolinska-Kempisty
Faculty of Chemistry, Wroclaw University of Science and Technology, Wroclaw, Poland
xxii List of contributors
Jun Su
State Key Laboratory of Mechanical Transmission, School of Materials Science and
Engineering, Chongqing University, Chongqing, P.R. China
Lidong Sun
State Key Laboratory of Mechanical Transmission, School of Materials Science and
Engineering, Chongqing University, Chongqing, P.R. China
Wae Zin Tan
Kajang, Malaysia
Jing Yuen Tey
Kajang, Malaysia
Hsin-Yu Tsai
Hui-Hsin Tseng
Department of Environmental Engineering, National Chung Hsing University, Taichung, Taiwan
Toshinori Tsuru
Department of Chemical Engineering, Hiroshima University, Higashi-Hiroshima, Japan
Kuo-Lun Tung
National Taiwan University, Taipei, Taiwan, ROC; Water Innovation, Low Carbon and
Environmental Sustainability Research Center (WInnER), National Taiwan University,
Taipei, Taiwan, ROC
Meng Wang
United States
Zhen Wang
Ming-Yen Wey
Department of Environmental Engineering, National Chung Hsing University, Taichung,
Taiwan
Kang Xiao
Beijing, P.R. China
Hao Xu
Beijing, P.R. China
List of contributors xxiii
Yirong Xu
Beijing, P.R. China
Jiaye Ye
Center for Automotive Electronics, Shenzhen Institute of Advanced Technology, Chinese
Academy of Sciences, Shenzhen, P.R. China
Tomohisa Yoshioka
Research Center for Membrane and Film Technology and Graduate School of Science,
Technology and Innovation, Kobe University, Kobe, Japan
Xingyi Zhang
Yangtze Delta Region Institute (Huzhou) & School of Physics, University of Electronic
Science and Technology of China, Huzhou, P.R. China
Preface
It has been over 60 years since the development of the first asymmetric poly-
meric membrane by Dr. Sidney Loeb and Dr. Srinivasa Sourirajan (University
of California, Los Angeles, United States) for seawater desalination. Research
in membrane science and technology has progressed rapidly over the past
decades, and many new and advanced materials (both organic and inor-
ganic) have been discovered and employed in the fabrication of membranes
and the modification of their properties. It is therefore of paramount impor-
tance to summarize the fundamental understanding of and information
about these membranes and their distinctive applications. In this book a
comprehensive overview of membrane technology is presented, from the
fundamental knowledge of fabrication principles and separation mechanisms
to a wide range of applications, including new and emerging processes.
In more detail, this book provides essential guidance for students, research-
ers, and scientists working in the field of membrane science and technology.
The fundamentals of membranes in different technologies, including their
working principles, transport mechanisms, and requirements for practical
applications, are discussed in this book. Key references and practical sources
are also provided, enabling an in-depth understanding of the numerous
aspects of membrane science and technology.
Furthermore, studies on membranes and their applications, such as in water
and wastewater treatment, chemical and biomedical processes, gas separa-
tion, and renewable power generation, are reviewed in this book. For
instance, recent advances in three-dimensional membranes for water appli-
cations, organosilica and metal-organic framework membranes for gas sepa-
ration, high-performance membranes for vanadium redox flow batteries
and vanadium-air redox flow batteries, ceramic membranes for fuel cells,
and membranes with enhanced safety for lithium-ion batteries are summa-
rized and discussed extensively. Recent advances in modeling and simula-
tions of different membranes and their components, such as spiral-wound
membranes and spacer-filled channels, are also included to provide better
insights.
xxvii
xxviii Preface
To facilitate a comprehensive characterization of membranes at different

levels, the book also presents the common testing methods, along with some
cutting-edge techniques for the accurate evaluation of the membrane proper-
ties and performances, which are of vital importance to the future develop-
ment of advanced membranes. For instance, the advanced characterization
for membrane surface fouling is discussed in detail.
Finally, to enable a better understanding of the latest trends and current
research on membrane technology, the most up-to-date details on the use of
advanced organic and inorganic materials and novel membrane fabrication
techniques for the development of membranes are also reviewed. The advan-
tages of these new materials along with the superiority of the newly devel-
oped fabrication methods in comparison to conventional strategies are also
extensively discussed.
This book will equip future researchers with the ideas and directions that
they need to understand the great potential and prospects of next-generation
membrane fabrication. It is also the aim of this book to reflect the ample
research activities and outcomes in the membrane field with an eye toward
global utilization and impact.
This book is an essential reference resource not only for students and
researchers but also for professionals and policymakers around the globe
working in three main sectors: academia, industry, and government.
We would like to express our gratitude to all the authors who contributed to
this book and shared their valuable state-of-the-art knowledge and experi-
ence with the associated topics. Last but not the least, we acknowledge the
professional staff of Elsevier for their continuous support.
Hui-Hsin Tseng1, Woei Jye Lau2, Mohammad A. Al-Ghouti3 and

Liang An4
1
Department of Environmental Engineering, National Chung Hsing University,
Taichung, Taiwan, 2Advanced Membrane Technology Research Centre (AMTEC),
School of Chemical and Energy Engineering, Universiti Teknologi Malaysia, Skudai,
Malaysia, 3Department of Biological and Environmental Sciences, College of Arts
and Sciences, Qatar University, Doha, Qatar, 4Department of Mechanical
Engineering, The Hong Kong Polytechnic University, Hong Kong, P.R. China
About the editors
Dr. Hui-Hsin Tseng is currently a Professor in the Department of

Environmental Engineering, National Chung Hsing University (NCHU),
Taiwan. She graduated with a degree in chemical engineering in 1997 and
earned her M.S. in 2000 and her Ph.D. in 2003 from the Department of
Environmental Engineering at NCHU. Recent research topics include the
development of inorganic membranes and nanomaterials for hydrogen pro-
duction and purification and carbon dioxide capture; the design of the mixed
matrix membranes for vapor permeation, gas separation, and oily wastewater
treatment; and the design of antifouling membranes for metal recovery and
water recycling from industrial effluents. Dr. Tseng has authored or coau-
thored 84 technical articles and three patents. She has been invited to serve
as a moderator or as an invited or keynote speaker at many international
conferences, including WFC12 in 2016, ISIM9 in 2018, and ICIM16 and
WFC13 in 2021.
Dr. Woei Jye Lau is currently an Associate Professor at the School of
Chemical and Energy Engineering, Universiti Teknologi Malaysia (UTM). He
obtained his Bachelor of Engineering in Chemical-Gas Engineering and his
Ph.D. in Chemical Engineering from UTM. Dr. Lau has a very strong research
interest in the field of membrane science and technology for water applica-
tions and has published more than 200 scientific papers with a total number
of Scopus citations exceeding 8000 and an h-index of 47. He is the book
author of Nanofiltration Membranes: Synthesis, Characterization and Applications
published by CRC Press. In addition, he is the editor of two research books
published in 2019 (Advanced Nanomaterials for Membrane Synthesis and Its
Applications, Elsevier) and 2018 (Advanced Materials for Membrane Fabrication
and Modification, CRC Press). Currently, Dr. Lau serves as a subject editor for
Chemical Engineering Research and Design (Elsevier) and as associate editor for
Water Reuse (International Water Association). In October 2020, Dr. Lau was
named among the top 2% scientists in the world, according to the Stanford
Report for 2019 published in the journal PLoS Biology.
Mohammad A. Al-Ghouti is a professor in environmental chemistry at the
Qatar University, Qatar. He obtained his PhD degree in environmental xxv
xxvi About the editors
chemistry from the Queen’s University of Belfast, United Kingdom. Prof.

Al-Ghouti was successful in securing funding for 10 external competitive
funds, 6 internal funds, and 3 industrial projects. Prof. Al-Ghouti has super-
vised 18 MSc and 9 PhD students. The focus of Prof. Al-Ghouti’s research is
to prepare and modify the surface of adsorbents and membranes, study the
adsorption mechanisms, and study the remediation behavior on various
environmental compartments, including areas of environmental chemistry,
membrane coating, membrane modification, controlling CaSO4 scaling, and
biofouling on reverse osmosis membrane, nanoparticles for water and wastewa-
ter treatment, multivariate, environmental remediation, waste minimization,
and treatment. In total, he has authored or co-authored over 198 peer-reviewed
research publications in environmental sciences and environmental sciences-
related journals and over 55 research abstracts and posters. He has published
two book chapters related to the field of environmental sciences. His current
Google Scholar Citation h-index is 39; i10-index is 90. According to a study
conducted at the Stanford University based on the (Scopus) database for the
years 2019 and 2020, Prof. Al-Ghouti has been listed among the top 2% of the
most influential scientists in the world in all sciences.
Google Scholar:
https://scholar.google.com/citations?user=TH7TGJ4AAAAJ
ResearchGate:
https://www.researchgate.net/profile/Mohammad_Al-Ghouti
Affiliation and Expertise:

Professor in Environmental Chemistry, Environmental Science Program,
Department of Biological and Environmental Sciences, College of Arts and
Sciences, Qatar University, Doha, Qatar
Dr. Liang An received his bachelor’s degree in thermal and power engineer-
ing from Harbin Institute of Technology and his Ph.D. degree in mechanical
engineering from the Hong Kong University of Science and Technology
(HKUST). After graduation he worked as a visiting scholar and a postdoctoral
fellow in the same research group. Currently, he is an Associate Professor at
HKUST. His research interests are in the area of clean energy conversion tech-
nologies and renewable energy storage technologies. His research interests
include fuel cells and batteries.
CHAPTER 1
Ionic liquidbased membranes for gas

separation
Eiji Kamio1,2,3
1
Center for Environmental Management, Kobe University, Nada-ku, Kobe, Japan,
2
Department of Chemical Science and Engineering, Kobe University, Nada-ku, Kobe,
Japan, 3Research Center for Membrane and Film Technology, Kobe University, Nada-ku,
Kobe, Japan CONTENTS
1.1 Introduction
............................ 1
1.1 Introduction 1.1.1 Ionic liquids .....2
1.1.2 Gas permeability
Over 20 years have passed since the need to reduce emissions of CO2 came to of room-temperature
ionic liquidbased
be viewed as a global issue. Although various schemes and technologies have
membranes ...............4
been developed to reduce CO2 emissions, atmospheric CO2 concentrations
continue to rise. To inhibit further increases, it is crucial to develop technology 1.2 Ionic
to separate and capture CO2 from exhaust gases emitted from various CO2 liquidbased CO2
separation
sources. To decrease atmospheric CO2 concentrations, the methods of CO2 membranes ....... 8
capture and storage; CO2 capture, utilization, and storage; and direct air cap- 1.2.1 Supported ionic
ture are considered effective. However, the cost of CO2 separation, including liquid membranes ... 10
the costs of energy, operation, and equipment, hinders the realization of these 1.2.2 Pressure-
CO2 separation technologies, and it is difficult to achieve efficient CO2 reduc- resistant ionic
liquidbased
tion using the currently available separation technologies. Therefore the devel- membranes ............. 11
opment of low-cost and energy-saving CO2 separation processes is necessary.
1.3 CO2-reactive
Steady progress has been made to improve conventional CO2 separation ionic liquidbased
methods, such as absorption and adsorption, to decrease their cost and energy facilitated-transport
use. However, chemical absorption, which is currently the most mature tech- membranes ..... 17
1.3.1 Design concepts
nology for CO2 separation, requires large facilities and large amounts of energy
of CO2-reactive ionic
to regenerate the absorbent. Hence it remains difficult to establish a compact liquids and CO2
decarbonization process for chemical absorption that can be applied to small permeation mechanisms
thermal power plants, chemical plants, and biogas purification processes. of CO2-reactive ionic
liquidbased supported
Membrane separation is considered a new class of CO2 separation methods, ionic liquid
with the potential to realize energy savings in CO2 separation. In addition, membranes ............. 17
the membrane separation method is expected to enable the establishment of 1.3.2 Amine-
functionalized ionic
compact, on-demand CO2 separation because membrane modules with high-
density membrane integration are possible. For these reasons, membrane 1
60 Years of the Loeb-Sourirajan Membrane. DOI: https://doi.org/10.1016/B978-0-323-89977-2.00009-9
© 2022 Elsevier Inc. All rights reserved.
2 CHAPTER 1: Ionic liquidbased membranes for gas separation
ionic liquid separation has attracted significant attention as a next-generation decarboniza-

membranes ............. 18 tion technology. However, to realize highly effective CO2 separation using
1.3.3 Amino acid ionic
membrane separation technology, high-performance CO2 separation mem-
ionic liquid branes must be developed with high CO2 permeance and high CO2 selectivity
membranes ............. 19 over other light gases such as N2, O2, H2, and CH4. Therefore many researchers
1.3.4 Supported ionic have recently attempted to develop high-performance CO2 separation mem-
liquid membranes branes and have achieved remarkable progress (Han and Ho, 2021; Lei et al.,
containing aprotic
2020; Tome and Marrucho, 2016; Tong and Sekizkardes, 2021; Yeo et al.,
heterocyclic anion
based ionic 2013; Yu et al., 2018; Zou and Zhu, 2018).
liquids ...................... 21 The available types of CO2 separation membranes include polymer mem-
1.3.5 Supported ionic
liquid membranes
branes, inorganic membranes, and supported liquid membranes. Recently,
containing ionic liquids multiple new concepts to improve the CO2 separation performance of these
with carboxylate membranes have been proposed and reported. For example, new polymer mem-
anions ...................... 22 branes using thermally rearranged polymers and polymers of intrinsic micro-
1.4 Ion gel porosity have been developed, with many researchers attempting to improve
membranes their selective CO2 permeability by precisely controlling the free volume on
containing task- the basis of molecular design (Lee et al., 2020). For inorganic membranes,
specific ionic many studies are currently being conducted to control selective permeability
liquids .............. 23
through precise pore-size manipulation by tuning the nanostructures of inor-
1.4.1 Ion gel
membranes containing ganic materials such as zeolites and silica (Funke et al., 2014; Yeo et al.,
amino acid ionic liquids 2013). Meanwhile, supported liquid membranes are undergoing new devel-
and aprotic heterocyclic opments using ionic liquids (Bara et al., 2009a; Scovazzo, 2009; Tome and
anionbased ionic Marrucho, 2016). While these types of CO2 separation membranes remain
liquids ...................... 23
under development, membranes with high CO2 separation performance
1.4.2 Ion gel
membranes with beyond the CO2/light gas selectivity and CO2 permeability trade-off, the
epoxy amine so-called Robeson upper bound, of conventional polymer membranes
gel networks ............ 25 have been successively reported.
1.5 Conclusion and Among these newly proposed CO2 separation membranes, in this chapter,
remarks ........... 26 ionic liquidbased CO2 separation membranes are outlined. The design cri-
References ....... 26 teria of an ionic liquid for the material of CO2 separation membrane, the
characteristics of several types of ionic liquidbased membrane, and the
CO2 separation performance of facilitated-transport membrane containing
an ionic liquidbased CO2 carrier are discussed.
1.1.1 Ionic liquids

Ionic liquid (IL) is a general term for organic salts that are capable of existing
as liquids even at temperatures of 100 C or less. ILs with melting points
below room temperature are specifically referred to as room-temperature ILs
(RTILs). These are novel solvents with completely different characteristics
from molecular liquids such as water and organic solvents, with expected
applications in various fields.
1.1 Introduction 3
Caons
Imidazolium Ammonium Phosphonium Pyridinium Pyrrolidinium
Anions
Chloride Bromide Bis(trifluoromethylsulfonyl)imide Alkylsulfate Triflate

(Tf2N–)
Tetrafluoroborate Hexafluorophosphate Dicyanamide Tricyanomethanide Tetracyanoborate

(BF4-–) (PF6–) (DCN–) (C(CN3)–) (B(CN)4–)
Aproc heterocyclic anions
pyrazolide Imidazolide 1,2,4-triazolide 2-cyanopyrolide indazolide

FIGURE 1.1
Typical cations and anions constituting ionic liquids.
The typical cations and anions that constitute ILs are summarized in Fig. 1.1.
Some RTILs can selectively dissolve CO2 and are under investigation for use
as CO2 separation media.
Owing to the strong Coulomb force between the cations and anions, ILs
have low, even negligible, evaporation pressures and are therefore almost
nonvolatile. Because of this nonvolatility, membranes containing an IL as the
CO2 separation medium do not exhibit volatile IL loss and can maintain
stable long-term performance. In addition, the ILs in the membranes do not
evaporate even at high temperatures. Most ILs have thermal decomposition
temperatures of 200 C or higher. Owing to their outstanding thermal stabil-
ity, ILs can be used even at high temperatures. These nonvolatile properties
and excellent thermal stability provide extreme suitability for use as constitu-
ents of gas separation membranes. Because of the strong Coulomb force act-
ing between the anions and cations, the polarity/nonpolarity, and the variety
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About nine o’clock we passed Gomba, inhabited by Fulahs, and
the capital of the district. Our guide Amadu evidently thought we
should stop there to see the chief, and showed great surprise at our
pressing on without a halt. To his discreet suggestions I turned a
deaf ear, and our interpreter seemed suddenly to have forgotten all
the Fulah language he knew. In the end our guide resigned himself
to the inevitable.
We had to make haste, for, reflecting on the causes of the check
we had received at Ilo, I was led to think that the English might have
had something to do with it, or, at least, that people who had been
amongst them—for the English themselves have no political
influence in these parts—had had intelligence enough to understand
and look after their interests. In the suite of the chief there was a
native of Bidda, who asked me to let him accompany me back to his
native place, but he too disappeared. In any case, however, as
Amadu told me, the news of our stay at Say had not yet reached
Gomba, still less Bussa, we might still, by pushing on rapidly,
circumvent the plans of those who were anxious to make mischief.
Forward then as rapidly as possible!
OUR GUIDE AMADU.
We soon passed the mouth of the Ngubi-Sokoto, of anything but

imposing appearance, but, as we were told, navigable at high water
for canoes until nearly up to the village from which it takes its name.
In the evening we had made more than 32 miles, the longest
distance achieved yet by the expedition in one day. We anchored a
little beyond Lanfaku.
Here we were visited by two parties of fishermen, who came to us
in canoes from the villages, such as are scattered about near all
important Fulah centres of population. The young men had their
heads shaved, but for a kind of tuft of hair left on the middle of the
upper part of the head, which was really not at all unbecoming.
Amadu told me that the Grunner expedition had been attacked on its
return from Gando at the village of Gesero, which was at war with
Gando. The inhabitants had tried to stop the guides of the Germans
by firing at them. Grunner had therefore burnt their village.
At ten o’clock we were overtaken by a tornado. We were back
again in the winter in fact, and every night there was a storm, or at
least a downpour of rain.
On the 29th we continued our forced march, passing several fine
villages surrounded by tatas. Kundji seemed a very big, strong place.
At about eleven o’clock we passed three rocks which probably
form part of a bar across the river when the water is low, marking the
beginning of the difficult and broken course below. At four o’clock we
anchored opposite Tchakatchi, on an island at the foot of a group of
magnificent baobabs. At the end of this island is a great mass of flint,
and the banks were strewn with the big rocks of polished granite we
knew so well. We were back again amongst the rapids, and had
once more to encounter difficulties such as we had conquered at
Ayoru and Kendadji. The whole village turned out to see us, and the
chief himself offered to act as pilot. I accepted his suggestion, for our
old Amadu had rather exaggerated his hydrographical knowledge.
The only garment of most of the men of the village was a little leather
apron worn behind, but some few wore drawers made of blue
Haussa cotton. The faces of the women were scarred in the same
way as those of their sisters of Kebbi, and they wore as ornaments in
the lobes of the ear, little pieces of white stick about a quarter of an
inch in diameter by seven inches long.
At seven o’clock the next day we started, preceded by the chief of
Tchakatchi, who steered a tiny little canoe with a paddle curiously
shaped and carved. The river was very much what we had expected
it would be the evening before, the rocks forming a regular
archipelago of islets, whilst rapids were also numerous. Fortunately
this state of things did not last long, and presently we came to an
almost calm reach, which brought us to Gilua, the capital of Yauri,
where we noted one very large hut, the residence of the chief of the
village.
I was in despair at having to travel like a bale of goods, without
being able to have any intercourse with the people whose country
we were passing through. But what could we do? Since we left Say
we had had no power to treat with the natives, our interpreters were
scarcely any good, whilst before us we had two great obstacles,
Bussa and the English.
According to the most recent information collected, it was at Gilua
and not at Bussa that Mungo Park died. Here then we had reached
the limit of the path he trod one hundred years ago, and I
remembered what Davoust had said to me: “Mungo Park has
become immortal through merely having tried to do what we shall
now endeavour to accomplish.”
I confess in all humility that since my return to France I have had
to change my opinion on that point.
On the left and right of the river there were two mountains
remarkable for their shape and their relative dimensions. I tried to
find out their names, but was told that they had none in particular. To
do honour to our comrades who had died under such melancholy
circumstances, I baptized them Mount Davoust and Mount
Delagarde, the latter having been the name of a naval officer who
died without reaching the Niger.
I trust that these names will be considered of good omen by
geographical critics in France, and that it will be admitted that I had
every right to choose them. Have not the English named all the
peaks of the chain on the banks of the river below Bussa after their
great men? Mount Davoust will look quite as well in our atlases as
Mount Wellington does in theirs.
We pushed on on the right between the villages of Ikum and
Rupia, and after passing a little rapid we anchored opposite a big
tree, beneath which a market was being held—an important one I
was told by the people of Rupia. The chief of Tchakatchi had told us
that we should meet his brother there, who would pilot us further, but
he had left that same morning. As usual the people began to shilly-
shally with us, and some men from Igga, whom we identified by their
white turbans embroidered with green, sold to them by the Royal
Niger Company, interposed in the conversation, but not in our favour.
“Off again!” was the word; we would push on and still push on,
alone and without a pilot or help of any kind, but we would not be
trifled with.
The people of Rupia are many of them Kambaris, a tribe alluded
to by Richard Lander. Their women when young go about quite
naked, and have the head shaved, but for a narrow tuft of hair left on
the top. They have the peculiar custom of dyeing their legs up to
above the knee with rocou, or red dye, which gives them the
appearance at a distance of wearing nothing but light red stockings.
This was the first occasion on which I had seen people in a state
of nudity in the Sudan, and this is the more remarkable as there are
plenty of stuffs to be had cheap at Rupia.
DJIDJIMA.
Noticing my astonishment, one of the beauties of the place made

the following naïve remark to me, which I thought was really rather
sensible: “Why should we wear clothes? Are we so badly made that
we need hide ourselves? All in good time, when we are old like our
mothers, we will make up for the loss of our physical advantages by
well-made clothes, but not till then.”
Many are the women on this earth of ours who could not say as
much!
A little mollified by what my young friend said, I still felt perfectly
furious at the sullen hostility and evident prejudice against us we
now constantly met with, which delayed our journey in a manner so
dangerous. Rightly or wrongly, I saw the hand of the English or of
their agents in it all. Fortunately, however, the river is easy of
navigation as far as Djidjima, a village picturesquely situated on an
island, opposite to which we anchored at four o’clock.
In the evening we went to the village, and I asked for a guide for
the next day, without much hope of getting one. I tried to win the
people over to my side by distributing a great many little presents.
We were invited to be present at a tam-tam, at which three dancers
performed, wearing leggings from which were suspended little bits of
iron resembling castanets, that made a deafening noise as they
struck against each other. The dancers, moreover, were very clumsy
in their attitudes.
No guide the next morning, but more men from Igga to stare at us.
The accounts that Amadu gives us of the difficulties of navigation
before us are heartrending, and as a matter of fact a little further
down, the river began to divide again into a great many arms. We
therefore anchored, and Digui went on in a canoe to reconnoitre.
Whilst he was away exploring we saw some eighty or a hundred
canoes going up an arm on our right, the tam-tam beating
ceaselessly. On inquiry we were told that it was only a water convoy
on the way to Rupia, where a very big market was about to be held.
All the way along the canoes stop to take up traders and their goods,
very much as the small steamers do on the Seine, or the omnibuses
in the streets of Paris. A canoe presently separated from the rest and
came towards us, its occupants saying very amiably that seeing we
had stopped, they had come to ascertain whether we were in any
difficulty, and to offer to guide us.
There is no doubt there is a good God for honest folk, I very
nearly added, and against the English. Be it remarked, for the reader
to draw his own moral, that everywhere the inhabitants of the little
villages, in a word the poor, helped us. The perpetual difficulties we
had to contend with in this part of our journey only arose in the big
centres.
THE NIGER BELOW RUPIA.
Delighted at this chance of going on, we started, our guides being

anything but de trop, passing several dangerous rapids and arriving
safely at Fogué, where the river became once more calm.
On October 2 we had a hard day, but it was the best before we
got to Bussa. Near Waro we had twice to go on in single file. The
force of the current was now immense, seven miles an hour at least.
Once more we felt as if we were dashing over cataracts, a painful
sensation we were all too familiar with. Our guide had met a friend,
who also to the best of his lights helped us to steer a right course. At
half-past five we reached Bussa, and anchored opposite the landing-
stage of the village. The river here divides into several arms, the
town being on that farthest to the right, about a mile from the bank. A
little village occupied by fishermen and traders was situated close to
our camp. The water, which is of a black colour, seems very deep
here, and the islands are covered with beautiful vegetation. The
natives approached us without fear, and we at once began to barter
with them in the usual manner, exchanging cloth, bracelets, rings
and beads for provisions.
I sent Amadu to greet the chief of the village, promising him a
good present if he succeeded in making that chief behave well to us.
I waited his return with impatience. There we were face to face
with our last but perhaps the greatest difficulty of our voyage. A very
considerable fuss is made about the cataracts or rather the rapids of
Bussa. Providence had so far befriended us, and enabled us to
reach this point without having lost one of our boats. Not a single
man, white or black, belonging to the expedition had lost his life
through what a year ago had been called our temerity. We had
managed everywhere with greater or less difficulty to pass on in
peace, leaving behind us none who had cause to hate us or to vow
vengeance on us. Yet one last effort, and our aim would be achieved
just as I had hoped to achieve it, exactly in accordance with our
instructions, in spite of all the difficulties thrown in our way, not only
by inanimate nature but by man. Just because this was to be our last
struggle we dreaded it more than we had done any other. I was
therefore immensely relieved when I saw Amadu coming back
accompanied by an emissary from the chief. According to him all
would go well, all was arranged; the chief of Bussa would supply us
with all we needed, and, greatly to the delight of our men, give us all
the help required for passing the rapids safely. A good supply of the
fruit called kus accompanied these cheering words. The chief would
receive us the next day.
Whilst I was chatting with our guide and the natives who
accompanied him, some girls were singing our praises and those of
their master. According to their songs the people of Bussa are
descended from the Persians, and they do in fact claim that they are
the children of Kisira, who fought with Mahomet, and were driven
away by him. Reference to history will show us that Kisira is only
another name for Chosroes the Great, who was, as a matter of fact,
the unfortunate adversary of the founder of Islam.
I state the fact for what it is worth, for the benefit of ethnologists.
A PALAVER.
THE SO-CALLED NIGRITIAN, THE OLD PONTOON OF YOLA.
CHAPTER X
FROM BUSSA TO THE SEA; CONCLUSION OF OUR
VOYAGE
The whole of the morning of the 3rd was occupied in receiving

visits from people more or less nearly related to the chief, and in the
afternoon I was informed that his Majesty himself would receive me.
We crossed a marsh between the village and the bank, and duly
arrived at Bussa.
There is nothing very imposing about the town, and it has been
recently much damaged by fire. We stopped at the door of a big
round hut, some thirty-five to forty-five feet in diameter, which was
really very well built. After a brief delay we were admitted.
The chief of Bussa was squatting on a bench of hardened earth,
some twenty inches high, and wore a bubu of doubtful cleanliness,
and a cap such as that worn by the eunuch in Molière’s play to which
I alluded in speaking of Dendi. The bench was covered with just
such a red carpet, with a lion rampant as I had seen at Tenda. The
chief’s spear was stuck in the ground beside him, and his sceptre
consisted of a cane ornamented with copper and silver. A horribly
ugly wife, with a face covered with scars, shared the royal bench,
whilst the courtiers remained squatted on the sand during the
interview. On entering the hut every one was expected to kneel, and
on reaching the chief the visitor had again to prostrate himself and
cast sand upon his own head.
VIEW OF BUSSA.
A wooden bench was assigned to us to sit on, and I spread out

the handsomest present I had brought with me.
Salutations were now exchanged. Thanks were given in the name
of the Sultan of the French for the help given to Captain Toutée the
year before by the Bussa canoes. I then slipped in a word about the
facilities of transport I hoped for for myself.
The reply was evasive, and moreover the expression of the chief’s
face was anything but intelligent. We returned on board.
The next day our visitors became more and more numerous.
Having shown off the phonograph to various persons, the rumour of
that wonderful instrument reached the ears of the chief himself, and
he sent word to me that he too would like to hear it.
NATIVES OF BUSSA.
He was, however, unwilling to put himself to any inconvenience

for the sake of it, and wished me to take it to him. Anywhere else but
at Bussa I would have said he might go to the devil, for it would be a
very delicate operation to take the phonograph to him, especially
across the marsh. But I was determined to do all in my power to
conciliate the chief, so as to have his aid when I crossed the rapids.
Four of my strongest coolies were therefore told off to carry the
instrument, which fortunately arrived without sustaining any damage.
The scene when I showed off the powers of the phonograph was
interesting, for while the attendants of the chief could not conceal
their surprise, he himself maintained his dignity, and his set features
expressed nothing but stupidity. He offered us a sheep, because he
said, “Now that we have been well amused, we must eat well.”
Trying to turn his good humour to account, I reverted to the question
I had at heart—the passage of the rapids. It appeared that my
question on the subject had not been understood the evening before,
at least so I was now given to understand. I repeated my request,
taking care this time to make my meaning perfectly clear. I wanted
Bussa canoes to take everything we had on board down below the
rapids to the village of Auru, as they do the merchandise of the
village. We ourselves could then pass down quite easily in our
lightened crafts with the guides I also asked for. I got a promise at
last that all my wishes should be met.
CANOES AT BUSSA.
On the 5th, however, there were still no canoes, but at four o’clock
the chief sent for me and told me that the whole thing was arranged
and settled. In fact, I heard him give the orders to two negroes, who
were, I was told, the chief canoe men. We agreed that I should pay
two hundred thousand cowries. Thinking that everything was really
settled this time, I gave the chief my own fowling-piece and a little
pocket revolver.
WOMEN OF BUSSA.
During the day more big canoes, from about twenty-seven to

thirty-three feet long, came alongside of our boats loaded with rice
and the native produce called karité. The English at Seba I was told
give two bags of salt for one of rice, and the karité which comes from
Rupia fetches a good price in the factories.
I must note here, en passant, how little we French know how to
make the most of what we have in our colonies. This karité, for
instance, which is a greasy substance extracted from the fruit of the
Bassia parkii, is to be obtained in immense quantities in the French
Sudan. It has been analyzed, and there has been a great deal of talk
about it in periodical literature, but not a pound of it has been
exported.
WOMEN OF BUSSA.
I had mentally fixed the 7th as the date for our departure from
Bussa, at whatever cost. We had now been there three days, and
the English must have heard of our arrival. How would they behave
towards us? I know that the Royal Niger Company is not particularly
scrupulous as to the means it employs, and of this there are plenty of
well-known instances: such as the torture of Mizon by Flint at
Akassa, after being wounded in a fight with the Patanis, who were
perhaps incited against him; or in the case of the foundering of the
Ardent, when her crew, deprived of fresh provisions, died off, the
Company showing not a scrap of compassion for them, or at least
not sending them any help.
TRUMPETERS OF BUSSA.
From the English point of view, it would be a fairer way of making

war to rouse the people of Bussa against us; but never mind, we
have cannon, rifles, and thirty thousand cartridges, so that although
the natives do own a certain number of quick-firing weapons, we
should be the ones to get the best of it in a fight.
What I really dread more than the open hostility of the Company is
a sham friendliness on their part. If they came to our aid, offering to
help us, even in spite of ourselves, it would only be a bit of clever
diplomacy on their part, really quite against our interests.
I knew that the English had a post at Leba, about forty-four miles
down-stream, and if there happened to be men enough there, they
might send a detachment up to us, to conquer difficulties they had
themselves perhaps created, when they would loudly declare that
they had saved our lives.
Should this take place, I feel pretty sure there are many in France
who would be simple enough to be taken in; such a thing has
happened before now, and I bet you anything you like, the English
will be warmly thanked. Remaining behind after we are gone too,
they will reap all the moral effect of our arrival from the Upper Niger;
the natives distinguish very little between the different white nations,
and it would be only too easy for the English to represent that we are
fellow-countrymen of theirs who have established themselves higher
up-stream.
If, therefore, we meant to succeed, and not to have our expedition
fail at the very entrance of the long-hoped-for haven, we must push
on as soon as possible, with or without the help of the natives. This
was the resolution come to by us five in a little council of war we held
together.
At four o’clock in the afternoon there was still no sign of a canoe.
The moment of decision had come. We had quantities of things in
our holds of little use or value, so I determined to lighten the boats as
much as possible, partly to lessen their draught, and partly to make it
easier to get at their bottoms to plug up any leak which should occur.
To begin with, there was all our ammunition, for except for a few,
used to practise shooting and to kill crocodiles, our store of thirty
thousand cartridges was intact. I decided to sacrifice twenty-two
thousand, and Digui, having found a place where the river was deep
enough not to dry up in the summer, our canoe went backwards and
forwards, and our men threw the cases into the river one by one.
The natives of Bussa ran to the banks and looked on in stupefied
astonishment; the copper cases gleaming in the sunshine excited
their cupidity.
Next we drowned many of our other stores. Into the water with our
bottles of oil and pots of pomade! Then into the fire with our celluloid
bracelets, necklaces, and rings! The despair of the natives on the
bank became deeper and deeper, reaching its height when, just to
wind up with éclat and to increase their regrets rather than from
necessity, we flung two or three dozen many-coloured umbrellas on
to the blazing pile. This produced positive desolation amongst the
spectators. All the better, it would teach them to behave properly to
foreigners.
A Fulah, sent I was told by the Sultan of Gando, flung himself at
my feet and entreated me to stop the destruction, assuring me that
the chief of Bussa would do all we wished. I reminded him of a
proverb current in his native place: “It is no good to put the fish back
in the water after it is cooked.” I had often been to that monarch’s
court, I added, and I had no time to begin all over again, probably in
vain, the palavers of yesterday and the day before that. I had had
enough of it now.
The river was falling too; we had noticed a decrease of some four
inches in the depth of the water during the last twenty-four hours,
and although all the natives agreed in declaring that it was only
temporary, I was not going to run the risk of finding our passage
blocked.
Amongst the crowd I noticed a diavandu from Igga, who was
trying to incite the natives against us. There were several of his
fellow-countrymen there too, easily identified by their bubus with the
green embroideries already referred to as sold by the Niger
Company.
I was now assured that the chief had had his canoe men put in
irons for disappointing us, but unfortunately a minute afterwards I
recognized them in the crowd.
I copy the following sentence from my journal written on the spur
of the moment—
WOMEN OF BUSSA.
“It is very evident that the English have not lost time since last
year; they have not, it is true, as I feared they would, pushed their
effective occupation up-stream, but have merely, so to speak, set
going the cavalry of Saint George. Their plan is simply to delay us;
yes, to delay us till it is impossible for our boats to pass the rapids.
We should then be obliged to go by land through Burgu, which they
know to be dangerous, and where they have no doubt sown
obstacles for us—one well-aimed shot, one well-planted poisoned
arrow, and there would be an end of our expedition and its results.
Otherwise there would be nothing left for us to do but to go down to
Leba and ask the English to co-operate with us.
“This was the policy described by Agoult, but Inch Allah! our rivals
will not have the latter satisfaction. Let us pass the rapids somehow
or other, and I promise myself that I will describe the odiousness of
such conduct even to, indeed especially to, the honest portion of the
English nation. The first thing to be done is to pass the rapids.”

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60 Years of the Loeb-Sourirajan

Membrane: Principles, New Materials,

Woei Jye Lau

For Information on all Elsevier publications

Publisher: Susan Dennis

List of contributors ................................................................................. xvii

Chapter 1 Ionic liquid based membranes for gas separation .................... 1

Chapter 2 Zwitterionic polymers in biofouling and inorganic fouling

Chapter 3 Recent advances in 3D printed membranes for water

Chapter 4 A 15-year review of novel monomers for thin-film composite

Chapter 5 Recent advances in high-performance membranes for

Chapter 6 Membranes for vanadium-air redox flow batteries................. 155

6.3 Membrane classifications..............................................................159

Chapter 7 Carbon membrane for the application in gas separation:

Chapter 8 Metal-organic framework membranes for gas separation

8.4 Computational efforts on metal-organic framework

Chapter 9 Advanced ceramic membrane design for gas separation

Chapter 10 Recent advances in lithium-ion battery separators with

10.5.2 Inorganic all-solid-state electrolytes........................ 292

Chapter 11 Silicon-based subnanoporous membranes with amorphous

Chapter 12 Ultrafiltration mixed matrix membranes: metal organic

Chapter 13 Zwitterion-modified membranes for water reclamation ...... 349

Chapter 14 Modelling of spiral-wound membrane for gas separation:

14.4.2 Effect of pressure drop in feed and permeate

Chapter 15 Modelling flow and mass transfer inside spacer-filled

Chapter 16 Transport model-based prediction of polymeric

Chapter 17 Molecular modelling and simulation of membrane

17.2.3 Interfacial polymerization .......................................... 476

Chapter 18 Advanced characterization of membrane surface fouling .... 499

Chapter 19 Reverse osmosis membrane fouling and its physical,

Chapter 20 Current status of ion exchange membranes for

Chapter 21 Reverse osmosis membrane scaling during brackish

21.3.2 Scaling types and morphology................................... 608

Chapter 22 Ceramic membrane in a solid oxide fuel cell based gas

INDEX ...................................................................................................... 651

Abdul Aiman Abdul Latif

Woon Chan Chong

Yie Kai Chong

Sher Ling Lee

Mohamad Fairus Rabuni

To facilitate a comprehensive characterization of membranes at different

Hui-Hsin Tseng1, Woei Jye Lau2, Mohammad A. Al-Ghouti3 and

Dr. Hui-Hsin Tseng is currently a Professor in the Department of

chemistry from the Queen’s University of Belfast, United Kingdom. Prof.

Affiliation and Expertise:

Ionic liquidbased membranes for gas

ionic liquid separation has attracted significant attention as a next-generation decarboniza-

1.1.1 Ionic liquids

Imidazolium Ammonium Phosphonium Pyridinium Pyrrolidinium

Chloride Bromide Bis(triﬂuoromethylsulfonyl)imide Alkylsulfate Triﬂate

Tetraﬂuoroborate Hexaﬂuorophosphate Dicyanamide Tricyanomethanide Tetracyanoborate

Aproc heterocyclic anions

pyrazolide Imidazolide 1,2,4-triazolide 2-cyanopyrolide indazolide

We soon passed the mouth of the Ngubi-Sokoto, of anything but

Noticing my astonishment, one of the beauties of the place made

THE NIGER BELOW RUPIA.

Delighted at this chance of going on, we started, our guides being

FROM BUSSA TO THE SEA; CONCLUSION OF OUR

The whole of the morning of the 3rd was occupied in receiving

A wooden bench was assigned to us to sit on, and I spread out

He was, however, unwilling to put himself to any inconvenience

During the day more big canoes, from about twenty-seven to

From the English point of view, it would be a fairer way of making