48632614

MEMBRANES AND MATERIALS FOR SEPARATION AND
PURIFICATION OF HYDROGEN AND NATURAL GAS
SEYED SAEID HOSSEINI
NATIONAL UNIVERSITY OF SINGAPORE
2009
MEMBRANES AND MATERIALS FOR SEPARATION AND
PURIFICATION OF HYDROGEN AND NATURAL GAS
SEYED SAEID HOSSEINI
(B. Sc., Chemical Engineering, Isfahan University of Technology)
A THESIS SUBMITTED
FOR THE DEGREE OF DOCTOR OF PHILOSOPHY
DEPARTMENT OF CHEMICAL & BIOMOLECULAR
ENGINEERING
NATIONAL UNIVERSITY OF SINGAPORE
2009
ACKNOWLEDEGMENTS
This thesis is the result of years of studies and research works carried out since I joined
the membrane research group at NUS. This provided me the wonderful opportunity of
working with great number of people whose contributions to this accomplishment
deserve special mention. It is my pleasure to take the chance and convey my sincere
gratitude to all of them herein:
In the first place, I am greatly thankful to my supervisor, Professor Tai-Shung Chung, for
his supervision, constructive advices and guidance from the very early stage throughout
the entire parts of this journey. Undoubtedly his constant demand enabled me to gain
extraordinary experiences in diverse aspects of the subject matters covering the areas of
my research. I also would like to extend my gratitude to Dr. Liu Ye for his kind supports
and valuable contributions in various stages of the research works.
Many thanks go in particular to Prof. K (William B. Krantz). I am much indebted to him
as a true teacher, and for his constant encouragements and supports in various aspects. I
really enjoyed every moments of working together and scientific discussions during the
development of EP technique.
I gratefully thank A/Prof. Hidajat, A/Prof. Hong and Dr. Jiang, for their constructive
comments on this thesis. I am thankful that in the midst of all their activity, they accepted
to be members of the examining committee.
i
Special thanks are due to my friends in membrane research group for their kind helps and
supports in countless occasions. Their company over these years made my stay at NUS
joyful and memorable. Dr. Li Yi is especially recognized for his kind mentorship at the
early stage of my research and teaching me valuable skills. I am also thankful to others
namely Ms. Low Bee Ting, Ms. Chng Mei Lin, Dr. Xiao Youchang, Dr. Lim Poh Chong,
Dr. Shao Lu, Ms. Peng Na, Mr. Lau Cher Hon for their valuable contributions and
assistance, especially at the later stage of my studies.
I was extraordinarily fortunate in receiving wonderful supports from Dr. A. Zadhoush,
Dr. S.S. Nouri and Dr. A. Mehrabani during the time I was at Isfahan University of
Technology. I could never have embarked and started all of this without their prior
teachings, trusts and encouragements. Thank you.
I gratefully acknowledge the International Graduate Scholarship (IGS) offered by Agency
for Science, Technology & Research (A*STAR) which provided me wonderful
opportunity pursue my graduate studies at the National University of Singapore (NUS)
through which I could realize abilities and discover other capabilities.
Sincere thanks are due to the Department of Chemical & Biomolecular Engineering
(NUS) and its staff for providing a positive, conducive and professional atmosphere for
research. Special thanks also go to the Institute of Materials, Research & Engineering
(IMRE) for providing me the opportunity of using their excellent facilities and research
environment throughout my studies. I really enjoyed being a research scholar affiliated to
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IMRE. I greatly acknowledge funding from NUS, A*STAR and National Research
Foundation (NRF) and other organizations and industrial partners whose financial
supports enabled this work to be successfully completed.
I would like to express my sincere thanks to the management at KEPPEL Offshore &
Marine Technology Centre (KOMtech) for their kind supports and patience which
undoubtedly played an important role in my concurrent progress in both academic and
industrial research.
Where would I be without my family? Words fail me to express my appreciation to my
parents and my sister for their love, dedication, prayers and inseparable supports,
especially in tolerating several years of my absence in pursuit of knowledge.
Last but not least, I must express my special thanks my family members for their love,
patience and endless encouragements and support. Acknowledgements are due to all
those who have assisted me in any way throughout the period of my PhD study.
Finally, I would like to thank everybody who was important and supportive in any
respect to the successful realization of this thesis, and express my apology if I missed
anyone in the list.
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TABLE OF CONTENTS
Page
ACKNOWLEDGEMENTS………………………………………………………………..i
TABLE OF CONTENTS………………………………………………………………...iii
SUMMARY…………………………………………………………….…………………x
NOMENCLATURE…………………………………………………………………….xvi
LIST OF TABLES………………………………………………………………………xxi
LIST OF FIGURES……………………………………………………………………xxiv
CHAPTER 1 INTRODUCTION TO GAS SEPARATION MEMBRANES 1
1.1 Historical Developments of Membranes 3
1.2 Industrial Applications of Gas Separation Membrane Technology 6
1.2.1 Hydrogen Separation 11
1.2.2 Air Separation 13
1.2.3 Natural Gas Treatment 14
1.3 Principles of Gas Separation Membranes 15
1.3.1 Membrane Materials 15
1.3.2 Membrane Design and Structures 21
1.3.2.1 Dense Versus Porous Membranes 21
1.3.2.2 Symmetric Versus Asymmetric Membranes 21
1.3.2.3 Dynamic in-situ Membranes 24
1.3.2.4 Liquid Membranes 25
1.3.3 Membrane Module Configurations 25
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1.3.3.1 Plate-and-Frame Membranes 26
1.3.3.2 Spiral Wound Modules 27
1.3.3.3 Hollow Fiber Modules 28
1.4 Transport Mechanisms in Gas Separation Membranes 30
1.4.1 Poiseuille Flow 31
1.4.2 Knudsen Diffusion 31
1.4.3 Molecular Diffusion 32
1.4.4 Solution-diffusion model 34
1.4.5 Gas Sorption and Diffusion in Glassy Polymers 34
1.4.6 Free Volume in Glassy Polymers 36
1.5 Research Objectives and Organization of Dissertation 38
1.6 References 43
CHAPTER 2 STRATEGIES AND APPROACHES IN DEVELOPMENT OF GAS
SEPARATION MEMBRANES 52
2.1 Key Limitations of Existing Polymeric Membranes 55
2.1.1 Permeability Versus Permselectivitiy 55
2.1.2 CO 2 -Induced Plasticization and Conditioning 57
2.1.3 Physical Aging 59
2.2 Molecular Design of Polymeric Membranes for Gas Separation 62
2.2.1 Tailoring Pure Polyimide Systems 62
2.2.2 Design of Block Copolymer Systems 70
2.3 Modification of Polymeric Membranes for Gas Separation 71
v
2.3.1 Polymer Blending 72
2.3.2 Hybrid Membranes 74
2.3.3 Thermal Annealing 77
2.3.4 Grafting and Halogenation of Polymer Backbone 79
2.3.5 Cross-linking Modification 81
2.4 Current and Future Developments 88
2.5 References 91
CHAPTER 3 ENHANCED GAS SEPARATION PERFORMANCE OF
NANOCOMPOSITE MEMBRANES USING MGO NANOPARTICLES 109
3.1 Introduction 109
3.2 Experimental 115
3.2.1 Materials 115
3.2.2 Membrane fabrication 116
3.2.3 Post-treatment of membranes 117
3.2.4 Membrane characterizations 117
3.2.5 Gas permeability measurements 118
3.2.6 Measurement of gas sorption 119
3.3 Results and discussion 120
3.3.1 Effect of MgO loading on the gas separation performance of
nanocomposite membranes 120
3.3.2 Effect of heat treatment on the gas separation performance of
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3.3.3 Effect of MgO nanoparticles on silver adsorption into the nanocomposite
membranes 127
3.3.4 Effect of silver treatment on the gas separation performance of
3.4 Conclusions 140
3.5 References 141
CHAPTER 4 HYDROGEN SEPARATION AND PURIFICATION IN
MEMBRANES OF MISCIBLE POLYMER BLENDS WITH
INTERPENETRATION NETWORKS 148
4.2.1 Materials 151
4.2.2 Preparation of dense flat membranes 153
4.2.3 Chemical modification of membranes 153
4.2.4 Characterization techniques 154
4.2.5 Gas permeability measurements 155
4.3.1 The miscibility and other characteristics of blends 156
4.3.2 Gas separation characteristics of blend membranes 158
4.3.3 Effect of chemical modification on performance of membranes 166
4.4 Conclusions 173
4.5 References 174
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CHAPTER 5 CARBON MEMBRANES FROM BLENDS OF PBI AND
POLYIMIDES FOR N 2 /CH 4 AND CO 2 /CH 4 SEPARATION AND HYDROGEN
PURIFICATION 179
5.2.1 Materials 184
5.2.2 Preparation of polymer precursors 185
5.2.3 Chemical modification of membranes 186
5.2.4 Preparation of carbon molecular sieve membranes 186
5.2.5 Characterization techniques 187
5.2.6 Gas permeability and sorption measurements 188
5.3.1 The physical and transport properties of polymers and blend precursors190
5.3.2 The effect of pyrolysis protocol on gas separation performance of carbon
membranes 194
5.3.3 The effect of temperature protocol on evolution of carbon molecular sieve
membranes 199
5.3.4 The effect of blend component on gas separation performance of
precursors and derived carbon membranes 201
5.3.5 The effect of blend composition on transport properties of carbon
membranes 206
5.3.6 The effect of chemical modification on properties and gas separation
performance of carbon membranes 215
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5.4 Conclusions 220
5.5 References 222
CHAPTER 6 DEVELOPMENT OF NOVEL HIGH-PERFORMANCE GAS
SEPARATION MEMBRANES THROUGH INTEGRATION OF POLYMER
BLENDING TECHNOLOGY AND DUAL-LAYER HOLLOW FIBER SPINNING
PROCESS 230
6.2.1 Materials 235
6.2.2 Dope formulation and preparation 237
6.2.3 Dual-layer hollow fiber spinning process 238
6.2.4 Silicone rubber coating and chemical modification 240
6.2.5 Membrane characterization and gas permeation tests 240
6.3.1 Morphological characteristics of dual-layer hollow fiber membranes 241
6.3.2 The effect of air gap distance on the morphology and gas transport
properties of dual-layer hollow fiber membranes 245
6.3.3 The effect of elongational drawing on the morphology and gas transport
properties of dual-layer hollow fiber membranes 251
6.3.4 The effect of outer layer dope flow rate on the morphology and gas
transport properties of dual-layer hollow fiber membranes 253
6.3.5 Anti-plasticization properties of dual-layer hollow fiber membranes 255
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6.3.6 The effect of chemical modification on the gas transport properties of
dual-layer hollow fiber membranes 257
6.4 Conclusions 259
6.5 References 261
CHAPTER 7 CONCLUSIONS AND RECOMMENDATIONS 276
7.1 Conclusions 276
7.1.1 Enhanced Gas Separation Performance of Nanocomposite Membranes
Using MgO Nanoparticles 277
7.1.2 Hydrogen Separation and Purification in Membranes of Miscible Polymer
Blends with Interpenetration Networks 279
7.1.3 Carbon Membranes from Blends of PBI and Polyimides for N 2 /CH 4 And
CO 2 /CH 4 Separation and Hydrogen Purification 280
7.1.4 Development of Novel High-performance Gas Separation Membranes
Through Integration of Polymer Blending Technology and Dual-layer Hollow
Fiber Spinning Process 282
7.2 Recommendations for Future Work 283
7.2.1 Nanocomposite membranes 283
7.2.2 Polymeric blend membranes 285
7.2.3 Carbon membranes from polymer blends 287
7.2.4 Dual-layer hollow fiber membranes from polymeric blends 288
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SUMMARY
Efficient technologies are required in various industries for separation of gas
molecules. Membrane-based gas separation has emerged as one of the fastest growing
technologies, due to the compactness, higher energy efficiency and economic advantages
which can be reaped. However, the inadequacy of the existing membrane materials
hinders the full exploitation of the application opportunities on the industrial scale. The
key challenges are developing membranes that can achieve good gas selectivity without
sacrificing gas permeability and also capable of maintaining the long-term gas separation
performance. Therefore, the purpose of this research study is to identify, explore and
develop viable techniques in order to address these challenges and provide membranes
with enhanced gas separation performance. A comprehensive research report is presented
encompassing various subjects including the development of new nanocomposite
membranes by using MgO nanoparticles with enhanced gas separation performance,
fabrication of membranes with interpenetration networks from miscible polymeric blends
for hydrogen separation and purification, production of carbon molecular sieving
membranes with enhanced performance for diverse gas separation applications and
fabrication of dual-layer hollow fiber membranes for gas separation in the semi-industrial
scale. Various instrumental analyses were employed in the course of this research for
characterization of physical and transport properties of developed membranes. The key
emphases were put on the natural gas treatment and hydrogen separation and purification.
Firstly, gas separation membranes with enhanced performance were developed by
the introduction of nano-size magnesium oxide particles followed by treatment with
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silver ions. Nanocomposite membranes were fabricated by incorporating nanoscale
magnesium oxide particles with different loadings into the Matrimid matrix. The addition
of MgO nanoparticles led to an increase in gas permeability of membranes; the highest
permeability was observed for the membranes containing 40 wt% MgO loading.
However, the selectivity of nanocomposite membranes was less than the neat Matrimid.
These changes can be mainly ascribed to the effect of pore dimensions of MgO
nanoparticles which are larger than the size range of gas molecules. Heat treatment at
temperatures below polymer glass transition temperature resulted in densified structure,
while heat treatment above T g resulted in further increase in gas permeability of
membranes through the changes in free volume of membrane. Secondly, nanocomposite
membranes with 20 wt% MgO were modified by silver treatment for stipulated periods of
time. A dipping procedure was adopted for this process which resulted in the
impregnation of silver ions into the nanocomposite membranes. It was found that the
major driving force for penetration of silver ions was offered by MgO nanoparticles and
polymer played the role of a carrier. The adsorption process was confirmed by different
techniques and oxygen sites at the surface of MgO were recognized to be responsible for
this process. The longer immersion time led to more silver adsorption into the membrane.
All the modified membranes exhibited enhanced gas separation performance for selected
gas pairs compared to the neat Matrimid membrane. The best performance was observed
for nanocomposite membranes (with 20 wt% MgO) after a 10-day silver treatment in
which the CO 2 /CH 4 and H 2 /N 2 selectivity increased by 50% and 35%, respectively. To
our best knowledge, this is the first study that combines the synergistic features of
nanocomposite structure and facilitated transport mechanism into a single membrane by
xii
using unique characteristics of MgO for gas separation. The results of this research study
were published in the J. Membr. Sci., 302 (2007) 207-217.
Another research study demonstrates the successful implications of blending
technique cum chemical modification for the fabrication of high performance polymeric
membranes for gas separation applications. The effect of variation in composition on
miscibility and microstructure, gas permeability and selectivity of blend membranes is
investigated. It is found that augmentation in PBI composition results in enhancement in
gas separation performance of membranes which is attributed mainly to the effect of
diffusivity selectivity. Analysis of the microstructure of membranes confirms the
variations in chain packing density, d-spacing and segmental mobility of polymer chains
as a result of blending. Separation performance of membranes is further ameliorated
through chemical modification of blend constituents. Modification of PBI phase with p-
xylenedichloride brings about slight improvements in selectivity performance, especially
for H 2 /CO 2 and H 2 /N 2 . In contrast, the selectivity of membranes is improved
significantly after cross-linking of Matrimid phase with p-xylenediamine. The results
indicate that higher tendency of Matrimid toward cross-linking reaction contributes more
in controlling the transport properties of membranes through diffusion coefficient by
increase in chain packing density and diminishing the excess free volumes. Results
obtained in this study reveal the promising features of developed membranes for gas
separation applications with great potential for hydrogen separation and purification on
industrial scale. To our best knowledge, this is the first study focusing the exploitation of
unique properties of blending high performance polymers of Matrimid and PBI for the
xiii
development of specialty membranes for hydrogen separation and purification. The
results of this research study were published in the Polymer, 49 (2008) 1594-1603. In
addition, a patent application (Ser. No.: 61/109,318) was filed on this subject in the U.S.
Patent Office.
Another research study features investigation on blends of poly(benzimidazole)
(PBI) and various polyimides regarding to their capabilities in formation of homogenous
blends with satisfactory morphology as precursors for carbon molecular sieve
membranes. Attempts are made to unravel the correlations between the pyrolysis process
parameters and separation performance of developed membranes. The results show that
compared to Torlon and P84, Matrimid is a better choice for preparation of blend
precursors in combination with PBI. The findings also suggest that carbon membranes
derived from PBI/Matrimid are congruous candidates for H 2 /CO 2 separation.
Interestingly, attractive performance for separation of other gas pairs was obtained by
tuning the PBI content in membranes. Modification of precursors by chemical cross-
linking prior to carbonization provides membranes with enhanced selectivity suitable for
separation of hydrogen from both nitrogen and carbon dioxide. This research study
accentuates the necessity and importance of adopting a proper strategy in exploiting
synergistic beneficial features of advanced materials (PBI), technology (polymer
blending), process (carbonization) and modification techniques (cross-linking) toward
achieving membranes with desired performance. Developed membranes surpass several
separation performance trade-offs with great potentials for various industrial applications
including CO 2 /CH 4 (α= 203.95), H 2 /CO 2 (α= 33.44) and particularlyN 2 /CH 4 separation
xiv
with unprecedented high permeability (P N2 = 2.78 Barrer) and selectivity (α= 7.99) for
this gas pair. To our best knowledge, this is the highest ever reported selectivity for this
gas pair. The results of this research study were published in the J. Membr. Sci., 328
(2009) 174-185. In addition, a patent application (Ser. No.: 61/103,547) was filed on this
subject in the U.S. Patent Office.
The final aspect of this research study focuses on the exploitation of polymer
blending technology in fabrication of high performance dual-layer hollow fiber
membranes. The functional material for the outer layer of the membranes is a blend of
PBI/Matrimid (50:50wt.%). Attempts are made to unravel the effect of various key
parameters on the morphological evolution, transport properties and separation
performance of the fabricated hollow fiber. The resultant membranes possess desirable
morphological structure, especially at the outer layer. It is important to note that all the
samples show the delamination-free structure at the interface between inner and outer
layers. The results suggest that increasing the air gap distance and spinning with
elongational drawing have improving effects on the gas permeance and selectivity of the
membranes. In contrast, increasing the outer dope flow rates resulted in membranes with
diminished gas permeance and altered separation performance depending on the air gap
distance. Application of silicone rubber coating was found an effective means for tuning
the gas transport and separation performance of the membranes. The findings also
indicate that chemical modification of as-spun hollow fibers, even for a very short period
of time, provides membranes with enhanced H 2 /CO 2 selectivity. Membranes fabricated
in this study essentially exhibit viable potentials for various gas separation applications
xv
including hydrogen and natural gas separation. Especially, fabricated membranes offer
H 2 /CO 2 selectivity values significantly higher than the intrinsic property of the blend
materials and with very good resistance against the CO 2 -induced plasticization.
xvi
NOMENCLATURE
A Effective area of the membrane (cm2)
Ag Silver
b Affinity of the gas molecules to the Langmuir sites
C Total penetrant concentration in the polymer (cm3(STP)/cm3(polymer))
C’ H Langmuir capacity constant
CD Concentration of gas adsorbed at Henry sites (cm3(STP)/cm3(polymer))
CH Concentration of gas adsorbed at Langmuir sites (cm3(STP)/cm3(polymer))
D Penetrant diffusion coefficient (cm2.s-1)
d Kinetic diameter of the gas molecule, inter-segmental spacing between two
polymer chains
D0 Pre-exponential factor for activation energy of penetrant diffusion (cm2.s-1)
D app Apparent diffusion coefficient
DD Henry’s diffusion coefficient (cm2.s-1)
DH Langmuir’s diffusion coefficient (cm2.s-1)
Dk Knudsen diffusion coefficient (m2.s-1)
dp Pore diameter (m)
ED Activation energy of diffusion (kJ.mol-1)
f Polymer dependant parameter
F Ratio of Henry’s diffusion coefficient to Langmuir’s diffusion coefficient
KD Henry’s dissolution constant (cm3(STP)/cm3(polymer).atm)
l Membrane thickness (cm)
Mw Molecular weight
xvii
n Integral number
P Permeability coefficient (1Barrer = 1 x 10-10 (cm3(STP).cm/cm2.s.cmHg)
p Pressure
P0 Pressure of the feed gas in up-stream (psia)
p2 Pressure at the upstream boundary
r Pore radius (m)
R Universal gas constant
S Solubility coefficient (cm3(STP)/cm3(polymer).cmHg)
S app Apparent solubility coefficient
T Absolute temperature (K)
Tb Boiling point (oC)
Tc Gas critical temperature (oC)
Tg Polymer glassy temperature (oC)
V Volume of the down-stream chamber of permeation cell (cm3)
V0 Volume occupied by the chains (cm3/g)
Vsp Specific volume of polymer film (cm3/g)
VW Van der Waals volumes (cm3)
W Mass fractions
α ij Separation factor between molecules i and j
θ Diffraction angle, diffusion time-lag
λ X-ray wavelength
ρ Density (g/cm3)
υ Average molecular velocity (m.s-1)
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Abbreviations
6FDA Hexafluoroisopropylidene-diphthalic anhydride
6FmDA 2,2-bis(3-aminophenyl)hexafluoropropane
6FpDA 2,2-bis(4-aminophenyl)hexafluoropropane
AFM Atomic force microscope
BET Brunauer-Emmett-Teller
BPDA 3,3’,4,4’-biphenyltetracarboxylic dianhydride
CA Cellulose acetate
CDA 3,6-diaminocarbazole
CMS Carbon molecular sieves
CMSM Carbon molecular sieve membranes
CTC Charge transfer complexes
DAF 2,7-diaminofluorene
DAFO 2,7-diaminofluorenon
DMEA N,N-dimethylaminoethyleneamine
DSC Differential scanning calorimetry
ECDA N-ethyl-3,6,-diaminocarbazole
EDX Energy dispersive X-ray
EtOH Ethanol
FFV Fractional free volume
FTIR Fourier Transform Infra-Red
FTM Facilitated transport membranes
xix
GC Gas chromatograph
IPDA Isopropylidenedianiline
Matrimid Poly [3,3’,4,4’-benzophenone tetracarboxylic dianhydride and 5(6)-amino-1-
(4'-aminophenyl-1,3-trimethylindane)]
MDA Methylenedianiline
mDDS 3,3’-diaminodiphenyl sulfone
MgO Magnesium Oxide
MMM Mixed matrix membrane
NMP N-methyl-2-pyrolidone
ODA Oxydianiline
o-Ps Orthopositronium
P84 Copolyimide of 3,3’4,4’-benzophenone tetracarboxylic dianhydride and 80%
methylphenylenediamine + 20% methylenediamine
PALS Positron annihilation lifetime spectroscopy
PAN Polyacrylonitrile
PBI Polybenzimidazole, poly [2,2’-(1,3-phenylene)-5,5’-bibenzimidazole]
PC Polycarbonate
pDDS 4,4’-diaminodiphenyl sulfone
pDDS 4,4’-diaminodiphenyl sulfone
PDMS Polydimethylsiloxane
PEO Poly(ethylene oxide)
PES Polyethersulfone
PI Polyimide
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PIM Polymers with intrinsic microporosity
PMDA Pyromellitic dianhydride
PPESK Poly(phthalazinone ether sulfone ketone)
P plas Plasticization pressure
PPO Polyphenyleneoxide
PPTI-1 Phenylene thioether
PSA Pressure swing adsorption
PSf Polysulfone
PSMA Poly(styrene-co-maleric anhydride)
PXDA p-xylenediamine
PXDC p-xylenedichloride
SEM Scanning electron microscope
TGA Thermogravimetric Analysis
UV Ultraviolet
WAXD Wide angle x-ray diffraction
wt. Weight
XPS X-ray photoelectron spectroscopy
XRD X-ray diffractometer
xxi
LIST OF TABLES
Table 1.1. Market development of membrane processes 7
Table 1.2. Future market of membrane gas separation 8
Table 1.3. Industrial applications of gas membranes 11
Table 1.4. Materials for gas separation membranes 17
Table 1.5. Qualitative comparison of various membrane modules 30
Table 2.1. Effect of meta or para linkages on gas separation performance (6FDA-based)
64
Table 2.2. Effect of connector groups on gas separation performance (6FDA-based) 66
Table 2.3. Effect of bulky substituents on gas separation performance (6FDA-based) 67
Table 2.4. Effect of polar functional groups on gas separation performance (6FDA-based)
68
Table 2.5. CO 2 /CH 4 separation performance of crosslinked dense films
85
Table 2.6. CO 2 /CH 4 separation performance of crosslinked hollow fibers 86
Table 3.1. Properties of magnesium oxide (MgO Plus) nanoparticles. 116
Table 3.2. The ideal selectivity of pure Matrimid and Matrimid-MgO nanocomposite
membranes with different nanoparticle loadings. 124
Table 3.3. The effect of heat treatment and cooling profile on the permeability and
selectivity of Matrimid-MgO nanocomposite membranes. 126
Table 3.4. XPS element binding energies of the neat Matrimid membrane before and after
silver treatment for 2 days. 130
xxii
Table 3.5. The effect of silver treatment on the permeability and selectivity of Matrimid-
MgO nanocomposite membranes. 135
Table 4.1. The permeability and ideal gas selectivity of polymer blend membranes with
various compositions. 160
Table 4.2. Gas diffusion coefficients and solubility coefficients of polyimide, blend
membranes and modified blend membranes. 161
Table 4.3. The effect of blend composition on the physical properties and fraction of free
volume of membranes. 163
Table 4.4. The effect of chemical modification using p-xylenedichloride on gas
permeability and selectivity of blend membranes. 169
Table 4.5. The effect of chemical modification using p-xylenediamine on gas
permeability and selectivity of blend membranes. 169
Table 5.1. The glass transition temperature of polymers and blend precursors measured
by differential scanning calorimetry (DSC). 191
Table 5.2. Gas permeability and ideal selectivity of individual polymers used in this
study. a,b 193
Table 5.3. The effect of pyrolysis temperature on gas permeability and selectivity of
carbon membranes made of PBI/Matrimid blend precursors.a,b 195
Table 5.4. The effect of blend components on gas permeability and ideal selectivity of
polymeric precursors.a,b 202
Table 5.5. The effect of blend components on gas permeability and ideal selectivity of
carbon membranes.a,b,c 204
xxiii
Table 5.6. Gas permeability and ideal selectivity of carbon membranes derived from
individual polymers.a,b,c 204
Table 5.7. The effect of blend composition on gas permeability and selectivity of
resultant carbon membranes.a,b,c 207
Table 5.8. The effect of application of a 5-day cross-linking modification by p-xylene
diamine (PXDA) on the gas transport properties of blend carbon membranes
with various compositions.a,b,c 217
Table 6.1. The spinning parameters and conditions used in preparation of dual-layer
hollow fiber membranes. 239
Table 6.2. Solubility parameters of the solvents, the coagulation agents and the polymers,
coagulation agents and polymers.* 243
Table 6.3. The effect of air gap distance on the gas permeance and separation
performance of dual-layer hollow fiber membranes. 247
Table 6.4. The intrinsic gas transport properties of the dense flat membrane made from
the polymer blend and respective individual polymers.a 250
Table 6.5. The effect of application of elongational drawing on the gas permeance and
separation performance of dual-layer hollow fiber membranes. 251
Table 6.6. The effect of variation in outer dope flow rates on the gas permeance and
separation performance of wet-spun dual-layer hollow fiber membranes. 254
Table 6.7. The effect of chemical cross-linking modification and its period on the gas
permeance and separation factor of dual-layer hollow fiber membranes. 258
xxiv
LIST OF FIGURES
Figure 1.1. Schematic diagram of gas separation process by a membrane 9
Figure 1.2. Trade-off line of oxygen permeability and oxygen/nitrogen selectivity 19
Figure 1.3. Typical membrane morphologies 23
Figure 1.4. Schematic drawing of a plate-and-frame module 27
Figure 1.5. Spiral wound elements and assembly 28
Figure 1.6. Hollow fiber separator assembly 29
Figure 1.7. Schematics of main mechanisms of membrane-based gas separation 31
Figure 1.8. Motion of gas molecules within the cavities through a series of diffusional
jumps 37
Figure 2.1. Robeson’s tradeoff curve for CO 2 /CH 4 gas pair
57
Figure 2.2. Diffusion of free volume and lattice contraction (physical aging) 61
Figure 2.3. General chemical structure of polyimide 63
Figure 2.4. Synthetic strategy for copolymer structure for CO 2 separation
71
Figure 2.5. Schematic of the various gas transport routes through hybrid polymeric
membranes 76
Figure 2.6. Amine modification of polyimides 79
Figure 3.1. Dispersion quality of MgO nanoparticles at the surface of the nanocomposite
membrane with 20wt% MgO. 121
xxv
Figure 3.2. The comparison of gas permeability for pure Matrimid and nanocomposite
membranes with different loadings of MgO nanoparticles. (left: permeability
of helium, hydrogen and carbon dioxide; right: permeability of oxygen,
nitrogen and methane). 122
Figure 3.3. The cross-section morphology of nanocomposite membranes with different
loadings of MgO nanoparticles. (MgO loadings: A: 20wt% B: 30wt% C:
40wt%). Inset: high magnification image of MgO nanoparticles inside the
polymeric matrix. 123
Figure 3.4. The elementary profiles of EDX analysis for the pure Matrimid and
nanocomposite membranes (20wt% MgO loading) after silver treatment for
different periods of time (Red peaks for Mg element, and green peaks for Ag
element). 129
Figure 3.5. XPS Ag 3d spectra of the nanocomposite membranes with 20wt% MgO
nanoparticles after silver treatment for different immersion times. 131
Figure 3.6. The schematic representation and molecular model for the adsorption of Ag
ions onto the oxygen sites at the surface of MgO. (Type of Interaction: Direct:
dotted lines, Secondary: dashed lines) 133
Figure 3.7. CO 2 sorption isotherms for the nanocomposite membranes before and after
silver doping. 138
Figure 3.8. The XRD spectra of the membranes before and after silver treatment with
different profiles. 139
Figure 4.1. Schematic representation of the chemical structure of polymers and hydrogen
bonding interaction between functional groups of Matrimid and PBI. 152
xxvi
Figure 4.2. DSC thermograms of the polymer blend membranes and individual
constituents. (a) 0, (b) 25, (c) 50, (d) 75, (e) 100 wt% PBI composition. 157
Figure 4.3. Composition dependency of Tg and comparison with theoretical values
predicted by Fox equation. 159
Figure 4.4. Analysis and comparison of the status of free volume in the structure of (a)
PBI and (b) Matrimid membranes using molecular simulation. 164
Figure 4.5. The XRD spectra of blends depicting the effect of composition on
microstructure of membranes. 165
Figure 4.6. (a) Proposed mechanism for the chemical cross-linking modification of
Matrimid component of blend using p-xylene diamine. (b) Chemical structure
of p-xylene diamine, (c) possible chain morphology and configuration of p-
xylene diamine cross-linked Matrimid. (cross-linking agents are specified by
circles).xylenediamine. 167
Figure 4.7. (a) Proposed mechanism for the chemical cross-linking modification of PBI
component of blend using p-xylene dichloride. (b) Chemical structure of p-
xylene dichloride, (c) possible chain morphology and configuraion of p-
xylene dichloride cross-linked PBI. (cross-linking agents are specified by
circles). 168
Figure 4.8. The XRD spectra of blend membranes cross-linked with p-xylene dichloride
(PXDC) and p-xylenediamine (PXDA) for different periods of time. 171
Figure 4.9. Molecular simulation analysis of chemical structure of cross-linking agents
(a) p-xylenediamine (b) p-xylenedichloride. 173
xxvii
Figure 5.1. Chemical structure of (a) Polybenzimidazole (PBI) (b) Matrimid® 5218 (c)
Torlon® 4000T and (d) P84. 185
Figure 5.2. Representation of carbonization protocols used in this study with three
distinct final temperatures; Protocol A: 600oC; Protocol B: 700oC; Protocol C:
800oC. 187
Figure 5.3. The elemental analyses of the polymeric precursor and derived carbon
♦ :(
membranes from PBI/Matrimid (50/50 wt. %) at various temperatures.
Carbon, ■ : Oxygen, ▲ : Nitrogen) 197
Figure 5.4. The effect of variations in pyrolysis temperature on microstructure of
PBI/Matrimid (50/50 wt.%) blend carbon membranes evaluated by X-ray
diffraction analysis. 198
Figure 5.5. The results of the thermogravimetric analysis carried out on blend precursor
PBI/Matrimid (50/50 wt. %) applying different temperature protocols. (a)
Protocol C (b) Protocol D (10oC/min). 200
Figure 5.6. The effect of blend component on structural characteristics of blend carbon
membranes evaluated by XRD analysis. (Pyrolysis temperature: 800oC) 205
Figure 5.7. Performance of PBI/Matrimid blend precursors with various compositions
and their corresponding carbon membranes for H 2 /CO 2 separation with
respect to trade-off line. (aData from Ref. [58]) 208
and their corresponding carbon membranes for N 2 /CH 4 separation with
respect to trade-off line. (aData from Ref [58]) (Trade-off line was drawn
based on data points collected from Ref. [62]) 209
xxviii
and their corresponding carbon membranes for CO 2 /CH 4 separation with
respect to trade-off line. (aData from Ref. [58]) 210
Figure 5.10. Plots of N2 and CH4 sorption isotherms for the carbon membrane derived
from the blend precursor composed of PBI/Matrimid (25/75 wt.%). (Pyrolysis
temperature: 800oC) 212
Figure 5.11. The effect of blend composition on structural characteristics of
PBI/Matrimid blend carbon membranes evaluated by XRD analysis.
(Pyrolysis temperature: 800oC) 213
and their corresponding carbon membranes with respect to trade-off line for
various gas pairs. (a) O 2 /N 2 (b) H 2 /N 2 (c) H 2 /CH 4 . (aData from Ref. [58])
214
PBI/Matrimid blend carbon membranes derived from cross-linked precursors.
(Pyrolysis temperature: 800oC) 219
Figure 6.1. The chemical structure of (a) Polybenzimidazole (PBI) (b) Matrimid® 5218
and (c) UDEL Polysulfone (PSf). 236
Figure 6.2. The trend of changes in dope viscosity as a function of polymer concentration
in the respective solvent. (♦ PBI/DMAc, ■ Matrimid/DMAc, ▲ PSf/NMP, ●
PBI:Matrimid (1:1)/DMAc) 238
xxix
Figure 6.3. Schematics of dual-layer hollow fiber spinning set-up and triple-orifice
spinneret. (a) dope fluid tank and pump; (b) bore fluid tank and pump; (c)
filter; (d) spinneret; (e) coagulation bath and (f) take-up drum. 239
Figure 6.4. SEM images illustrating various morphological aspects of a typical dual-layer
hollow fiber membrane (sample B): (a) membrane cross-section; (b)
membrane sector; (c and d) inner and outer layers; (e) interface region; (f)
outer surface of the outer layer and (g) inner surface of the inner layer. 242
Figure 6.5. The cross-section morphology of dual-layer hollow fiber membranes spun at
different air gap distances. 246
Figure 6.6. The trend of changes in CO 2 permeance as a function of upstream pressure
for silicone rubber coated dual-layer hollow fiber membranes.
256
xxx
CHAPTER ONE
INTRODUCTION TO GAS SEPARATION MEMBRANES
Over the last few decades, membrane science and technology has been facing
revolutionary era in many aspects. During this period, substantial scientific advancements
have been achieved resulting in evolution of numerous applications for membranes.
Among these, one may witness pronounced strides in the use of membranes for
separation of gases. Particularly, an extensive growth can be observed in various energy
sectors where gas separation membranes are widely used. This is perhaps, due to the
substantial rise in demand for various energy resources among which natural gas and
hydrogen are considered as viable and promising candidates, respectively. The
advantageous features of natural gas as an appropriate alternative to the oil have attracted
the interests toward further exploration and development of gas reserves. However, the
beneficial exploitation of natural gas may require overcoming some of the challenges.
One of the key issues which has impeded the widespread exploitation of discovered
natural gas resources is that majority of these fields suffer from contaminations with
species other than the desired product; which is methane. As a result, various gas
separation and purification technologies have been developed to address this issue and
make the development of the gas field feasible. Although the readily established
technologies have been very successful, their application has always been associated with
1
high energy intensity, high operational risk and large footprint. In many cases, these
shortcomings may cause limitations in design and operation of a proper gas separation
unit for specific fields. In this respect, the emergence of membrane technology has
attracted many attentions since its unique features can readily address some of the
challenges associated with conventional technologies.
Despite the presence of various types of membranes with organic or inorganic
roots, more attentions have been toward the development of gas separation membranes
from organic materials. This is mainly due to their advantageous features like availability
of raw materials, ease of processing and possibility for further modification of properties
in order to meet the desired specifications. Over the time, various engineering polymers
such as cellulose acetate, polyimides, polysulfones have undergone extensive studies for
their potentials as high performance membranes for gas separation applications. The
results obtained from these studies have provided good guidelines for material selection
and other important steps required for design and engineering of successful gas
separation membranes. The following section will provide an overview on the historical
development of membranes and how the basic concepts have emerged. Gas separation
membranes and their industrial applications will be introduced. The key features of
membrane technology for gas separation, their advantages and shortcomings compared to
the other contenders will be discussed.
2
1.1 HISTORICAL DEVELOPMENTS OF MEMBRANES
The origin of membranes and the associated phenomena dates back to the
eighteenth century. It was during that time that the basic ideas about membranes were
initiated due to the work of philosopher scientists. The word osmosis was among the
early terms coined by Abbé Nolet (at 1748) to describe the permeation of water across a
diaphragm [1]. It was during early 1830s that Mitchell reported some membrane
phenomena which were very interesting at that point of time [2]. He observed during his
laboratory experiments that natural rubber balloons deflated at different rates when
exposed to different gases. A membrane, in basic terms, is defined as a functional thin
film acting as a barrier between two mediums. Basically, the ability to control the
permeation of chemical species is considered as the essential property associated with
any membrane. For example, considering gas separation membranes, the separation is
typically achieved based on a mechanism that one of the components of the feed gas
permeates the permselective membrane at a much higher rate than the other species. The
driving force for this process is typically the pressure or chemical potential difference
between the feed and permeate sides.
In 1833, Graham reported his observations on the osmosis of an air-carbon
dioxide gas system through a wet animal bladder [3]. Almost two decades later, in 1855,
a systematic series of experiments was conducted by Fick aiming to investigate the gas
transport properties of membranes. These studies were carried out using nitrocellulose
membranes and resulted in development Fick’s First Law which has been of paramount
3
importance as a fundamental formula [4]. In 1866, T. Graham extended the Fick’s
experiments and could quantitatively measure the gas permeation through a membrane.
This experiment resembled the Mitchelle’s but was carried out in vacuum environment
rather than air [5,6]. The results obtained led Graham to propose the “solution-diffusion”
as the governing mechanism in transport of gas molecules through a membrane. In 1879,
S. von Wroblewski defined the permeability coefficient for membranes as the penetrant
flux normalized by pressure and thickness [7]. He also further characterized the
permeability coefficient and demonstrated it as the product of diffusivity and solubility
coefficients. In 1891, Kayser showed the validity of Henry’s law for the absorption of
carbon-dioxide in rubber [8].
All these laboratory experiments for about two centuries assisted in development
of fundamentals and theories of membrane science. This period took about two centuries
in with almost no tangible applications or product from membranes. It eventually turned
into reality and the first industrial and commercial applications of membranes were
emergence at early 20s. It was till only about five decades ago that the intensified
scientific research efforts eventually turned true and a technology based on membranes
was emerged. This breakthrough led to the gain of many attentions for further
development of membranes for various applications including but not limited to
separation of gaseous species.
Although the potentials of membranes for separation of gas mixtures was
identified long time ago, but the majority of the achievements can be traced to only few
4
decades ago. The fundamental efforts in this field took place during 1930s and 1940s
during which membranes from natural polymers were studied to understand the effects of
structure and molecular properties on the gas transport properties [9]. The research
activities were continued in the following decades and many other materials underwent
investigations for their potentials for gas separating membranes. These efforts were along
with the revolutionary development in testing equipments and measurement methods for
analysis and evaluation of membranes. Despite these progressive efforts, the emergence
membranes for practical gas separation applications was still suffering from the lack a
proper technology for fabrication of high performance membranes and modules. The
work by Loeb and Sourirajan in formation of asymmetric membranes from cellulose
acetate for reverse osmosis was a breakthrough which gave a lot promise for viability of
membranes for industrial applications [10]. In this respect, successful extension of
asymmetric structure concept to membranes in the shape of hollow fibers along with the
supplementary process developments for fabrication of defect-free composite membranes
played prominent roles to bring the science of gas separation membranes closer to a
potential technology [11,12].
Interestingly, it was only during the 1980s that gas separation using membranes
eventually turned into reality as a commercially available process. Hydrogen separating
membranes branded as “Prism” (manufactured by Permea) was the first product of its
kind to entre to the market and was coined as the first large industrial application of gas
separation membranes. Since then, membrane-based gas separation has undergone
substantial growth targeting various industrial processes and has become a $200
5
million/year business. The breakthrough that lead to this achievement was emerged based
on pioneering works in the field of reverse osmosis process through which high-flux
anisotropic membranes possessing large-surface-area had been successfully produced.
This development was of great success and the technology was rapidly adopted for
implementation in number of chemical plants. It was only few years later that a new
application was introduced which was the development of cellulose acetate membranes
for removing carbon dioxide from natural gas. It was at about the same time that
membranes were developed for certain air separation applications which could enrich
oxygen or nitrogen. This application has undergone rapid development over the years.
Finally, it can be found in the industry that membranes are also being used for variety of
small but growing applications such as hydrocarbon recovery and dehydration of
compressed air.
1.2 INDUSTRIAL APPLICATIONS OF GAS SEPARATION MEMBRANE
TECHNOLOGY
Separation technology constitutes one of the key components of the industrial
world covering diverse fields including chemical technology. Several separation
technologies have been developed upon the demand in unit operations. Some of them
such as distillation, crystallization, adsorption, absorption solvent extraction, etc are well
matured in certain application [13]. In comparison, membrane technology is considered
as a relatively new comer that has drawn many attentions, especially in recent years.
Membrane-based separation processes have undergone major developments since the
6
early days at about four decades ago. Various types of membrane separation units have
been developed and are in operation now for industrial applications and there are many
interests for further implementations or extension to other sectors.
Membrane is basically a semi-permeable barrier within which the separation is
taken place through the controlled rate of material transport. Membranes can perform
separation between liquid, gaseous or liquid/gas phases. In fact, membrane technology
has been largely in use for separation of liquid/liquid and liquid/solids through processes
like reverse osmosis, ultrafiltration, microfiltration, pervaporation, hemodialysis,
electrodialysis and controlled drug delivery. Table 1.1 provides the market growth for
various membrane processes in the final years of the last century.
Table 1.1. Market development of membrane processes
Sales (US$ Million)

Membrane process Annual growth
1996 2000
Dialysis 1300 2100 10
Microfiltration 600 960 10
Ultrafiltration 350 560 10
Reverse osmosis 250 450 12
Gas exchange 160 260 10
Gas separation 120 250 15
Electrodialysis 80 130 10
Miscellaneous >5 >10 7
Total 2940 4810 >10
The numbers may indicate a relatively small market share for gas separation
7
membranes compared to other membrane applications. However, this might be justified
by taking the young age of gas separation membranes into the considerations.
Nevertheless, with the current intensive research and development programs, particularly
in membrane materials, a bright and promising future is anticipated for gas separation
membranes. This can be highlighted by possessing the largest annual growth of 15%. The
estimated market growth in various industrial applications of gas separation membranes
are shown in Table 1.2 [14].
Table 1.2. Future market of membrane gas separation
Market (US$ Million @ 2000)

Separation
2000 2010 2020
Nitrogen from air 75 100 125
Oxygen from air <1 10 30
Hydrogen 25 60 150
Natural gas
CO 2 30 60 100
NGL <1 20 50
N 2 /H 2 O 0 10 25
Vapor/Nitrogen 10 30 60
Vapor/vapor 0 20 100
Air dehydration/other 15 30 100
Total 155 340 760
It can be found that nitrogen enrichment, CO 2 removal from natural gas and hydrogen
separation and purification constitute the dominant applications of gas separation
membranes. Nevertheless, a huge application cum market growth and expansion is
predicted for the use of membranes in refinery, petrochemical and natural gas industries.
8
Unlike the other essentially liquid phase applications, membranes for gas
separation act as a barrier interposed between two phases and perform a selective
separation through provision of certain degrees of restriction upon targeted species
[15,16]. Number of mechanisms has been identified for gas separation process in
membranes which will be discussed in subsequent sections. Generally in membrane gas
separation processes, the bulk phases are gas mixtures. Gas permeation is a set of
physical phenomena where certain gas components selectively pass through a membrane
where one of the species in the mixture is allowed to be exchanged in preference to
others. Separation of a gas mixture occurs since each type of molecules diffuse at a
different rate through the membrane. One bulk phase is enriched in one of the species
while the other phase is depleted of it [17]. The movement of any species across the
membrane is caused by one or more driving forces. These driving forces arise from a
gradient of chemical potential due to concentration gradient or pressure gradient or both.
An illustrative schematic of a two-phase gas separation is shown in Figure 1.1. Today,
large-scale membrane gas separation systems have found acceptance in many sectors of
industry.
Figure 1.1. Schematic diagram of gas separation process by a membrane

9
Membrane technology compares favorably with other conventional separation
techniques due to its multidisciplinary character of more capital and energy efficient. The
specific features and inherent advantages of membrane separation process can be
described as follows [16,18,19,20,21]:
1. Process simplicity in installation and operational
2. Low capital outlay and energy consumption as often only a compressor is required
without any additional utilities.
3. Compact size, small footprint and modularize capability which offer great savings
in space and weight.
4. System flexibility and easy scalability for various process capacities.
5. Mild operational condition (temperature, pressure, etc) in majority of application
6. Membrane separation can be carried out continuously.
7. Membrane properties can be adjusted “tailor-made” to meet specific requirements
or based on a desired task.
8. Membranes are compatible with other unit operations and can easily be integrated
as part of any complex separation processes.
Membrane gas separation process found its first industrial application by emergence of
PRISM® in early eighties [22]. This was for hydrogen separation and since then various
other applications have attracted attentions and grown rapidly. Table 1.3 lists the
multitude applications of gas separation membranes which will be discussed in the
followings sections.
10
Table 1.3. Industrial applications of gas membranes [23,24]
Gas Separation Application

O 2 /N 2 Oxygen enrixhment, nitrogen (inert gas)
generation
H 2 /Hydrocarbons Refinery hydrocarbon recovery
H 2 /CO Syngas ratio adjustment
H 2 /N 2 Ammonia purge gas
CO 2 /Hydrocarbons Acid gas treatment, enhanced oil recovery,
landfill gas upgrading
H 2 S/Hydrocarbons Sour gas treatment
H 2 O/Hydrocarbons Natural gas dehydration
H 2 /Hydrocarbons Helium separation
H 2 O/Air Air dehydration
He/N 2 Helium recovery
Hydrocarbons/Air Pollution control, hydrocarbon recovery
Hydrocarbons from process streams Organic solvent recovery, monomer
recovery
1.2.1 Hydrogen Separation
Hydrogen is anticipated to play an inevitable role as one of the promising sources
of energy in the future. The major proportions of produced hydrogen are used to supply
the refinery and fertilizer industries. The constant increasing demand for highly purified
hydrogen has resulted in attracting more attentions for extensive research studies on
advancement of the technologies for generation of hydrogen with higher efficiency and
lower production cost.
At present, steam reforming of hydrocarbons is predominantly the established
11
technology for generation of hydrogen and it supplies about half of the world’s demand
for this viable gas. In this process, a stream of natural gas mainly composed of methane
undergoes a water gas shift reaction. The yielded product has to be further processed in a
separation process in order to remove unwanted carbon dioxide and other byproducts
from the mixtures with hydrogen. Currently, commercially available separation processes
for this purpose are pressure swing adsorption, amine absorption and absorption using
aqueous solution of potassium carbonate which are highly energy intensive.
Hydrogen separation is known to be the first large scale application of membranes
for gas separation that took place in an ammonia plant. Survey has shown that separation
of hydrogen from nitrogen, ammonia, methane, coal together with syngas molar ratio
adjustment and other refinery applications totally account for 25% market share of
hydrogen separation by membrane technology [25,26]. Hydrogen separation has been
effectively carried out through polymeric membranes enjoying the advantageous
extremely high diffusion coefficient of hydrogen and its smaller molecular size compared
to other gas molecules [27]. However, the hydrogen separation and purification,
especially in refinery applications has been fraught with some difficulties like poor
reliability, fouling, plasticization, and condensation of hydrocarbon vapors [14]. This
highlights the need for development of new hydrogen-permeable membrane materials
with the capability to operate at high hydrocarbon partial pressures and high
temperatures. Another recommended approach for protection of the membrane is the pre-
treatment of the feed gas to reduce its dew point.
12
1.2.2 Air Separation
Air separation constitutes about 60% of overall membrane-based gas separation as
oxygen and nitrogen are considered as third and fifth largest bulk chemicals produced
worldwide [25]. Membrane based gas separation seems to be extremely attractive for the
enrichment of nitrogen from air which can economically produce nitrogen with purities
of up to 95%. The market share of membrane technology in producing nitrogen is
currently 30% of total production volume and growing. The first membranes used for this
purpose had O 2 /N 2 selectivity of about 4. Membrane modules constitute only about 20%
of the component cost of a nitrogen separation plant and the rest is spent for air
compressor. Thus, besides the improvements in membrane performance, reduction in size
of the feed gas compressor seems to be the key in lowering the nitrogen production costs.
In contrast, the overall efficiency of oxygen production using membranes highly relies on
the improvements in membrane performance. Essentially all approaches for production of
oxygen are based on oxygen-permeation while nitrogen-rejection process. Due to the
partial permeation of nitrogen molecules along with oxygen, pro ones production of pure-
oxygen has been facing difficulties and mostly the product is oxygen-enriched air with
purities in the range of 45-50% [28]. Therefore, due to the large industrial demand for
ultra-pure oxygen, oxygen production via membrane technology has yet to compete with
other rivals like cryogenic distillation and vacuum swing adsorption which can provide
oxygen with purities of about 99.999% and 95%, respectively [29]. Evaluations shows
that, in ideal case, new membrane materials with permeability of 250 (Barrer) and
separation factor of 4-6 would be required to make membrane as an attractive choice for
this application.
13
1.2.3 Natural Gas Treatment
Natural gas has undoubtedly become a viable choice in recent years due to the
high rises in the price of crude. The US production of natural gas has been evaluated to
20 trillion scf/year while the world production is about 50 trillion scf/year. Methane is the
key and most desirable component of natural gas, but it also contains impurities like
ethane, propane, butane, water, carbon dioxide, nitrogen and hydrogen sulfide which
have to be removed to certain levels before delivery to pipelines. Despite the dominant
presence of absorption separation by amines, use of membranes has been accepted as a
promising technology for natural gas treatment [30]. High efficiency is observed in
upgrading of natural gas by CO 2 , H 2 O and H 2 S removal using membranes. However,
membranes usually suffer from plasticization in the presence of trace quantities of
condensable heavy hydrocarbons and CO 2 [31]. Therefore it is an imperative to develop
robust materials which can resist plasticization and help the widespread application of
membranes for natural gas treatment.
For water removal from natural gas or dehydration, membrane technology
competes with glycol absorption process. The advantages of membranes are being more
environmental friendly and energy efficiency. Additionally, membranes can effectively
be used for separation of olefinic and paraffinic hydrocarbons. For example, separation of
ethane/ethylene and propane/propylene are very important processes in petroleum
refining and petrochemical industries as the extracted olefins are the major feedstocks in
production of petrochemical products such as polyethylene, polypropylene and other
copolymers [32,33]. Compared to low temperature distillation which is widely practiced
14
for olefin/paraffin separation, membrane technology enjoys large energy efficiency,
simpler operation, lower power consumption and less capital investment.
1.3 PRINCIPLES OF GAS SEPARATION MEMBRANES
With development of advanced technologies, effectual membrane separation processes
are required to address the immediate market challenges and requirements. It is
formidable that the supplied membranes be economically and technologically viable and
satisfies the gas separation productivity and efficiency. Therefore one may consider and
define the following items as the key components in development of successful gas
separation membranes, viz:
- Membrane material selection
- Membrane preparation and modification
- Membrane characterization and evaluation
- Membrane module design
Nevertheless, fundamental concepts have been always considered as the cornerstone at
anytime during the developments. Following sections aim to address some of the key
issues in this regard.
1.3.1 Membrane Materials
Perhaps this component constitutes the most important part of the membrane-
based gas separation process. It is well known that any specific gas separation application
requires materials with certain performance characteristics. For example it is found that
15
chemical interaction between a membrane material and a gas penetrant strongly affects
the separation efficiency of the membrane process [34]. Basically, the choice of proper
material is based on the specific properties originating from its nature and structural
factors. The key requirements of an effective membrane material may include: (1) high
separation efficiency with reasonable high flux, (2) good chemical resistance (3) good
mechanical stability (4) high thermal stability (5) engineering feasibility (6) satisfactory
manufacturing reproducibility (7) low cost [35,36]. Essentially the capital cost of a
membrane separation is beholden to the total membrane area required to perform the
separation for a specific amount of the gas. In practice, many gas feed streams are
contaminated with chemically reactive organic vapors (aromatic compounds, lubricating
oils and solvents) that potentially has adverse effects on membrane material through
swelling or dissolving. Thus, a membrane must have strong chemical resistance
properties and capable of enduring the environment exposed. Since pressure difference is
the driving force for separation, membrane materials have to maintain the mechanical
rigidity against the stress applied. Similarly, excellent thermal stability is required to
withstand the high operating temperatures. Conclusively, an ideal material should be
easily converted to cost effective membrane structure as well as possessing the intrinsic
characteristics of high permeability, selectivity and durability. The science and
technology for membrane materials has seen rapid developments over the past decades
and new materials with different structures have been tailor-made to perform the specific
separations. These developments have been for both organic and inorganic materials. The
following Table provides a list of successfully developed membrane materials for gas
separation.
16
Table 1.4. Materials for gas separation membranes [37]
Organic (polymeric) materials Inorganic materials

Polysulfone (PSf), Polyethersulfone (PES) Carbon molecular sieves (CMS)
Cellulose acetate (CA) Nanoporous carbon
Polyimide, Polyetherimide Zeolites
Polycarbonate [brominated] (PC) Ultramicroporous amorphous silica
Polyphenyleneoxide (PPO) Palladium alloys
Polymethylpentene Mixed conducting perovskites
Polydimethylsiloxane (PDMS)
Polyvinyltrimethylsilane
Basically, among the two available classes of membrane materials amorphous polymers
have been found to possess good processability, sufficient productivity and selectivity
while being cost-effective. Therefore polymeric membranes are of great promise for
industrial applications. In polymers, gas transport and intrinsic permeation characteristics
are significantly governed by the structure and configuration of macromolecular chains.
Glass transition temperature is one of the key characteristics that determine the state and
subsequently the properties of a polymer. In the glassy state, in which polymer is present
above its T g , the polymer structure is hard and rigid and it becomes soft and flexible
when the conditions change to the rubbery state. In fact, glass transition temperature
denotes the boundary between these two states and the temperature in which thermal
expansion coefficient undergoes drastic changes.
Compared to glassy polymers, generally the gas diffusivity thus the productivity
in rubbery polymers is high. However, this is achieved at the cost of low separation
17
efficiency resulted from the small contribution of diffusivity selectivity. On the other
hand, the low segmental mobility and long relaxation time are of the main characteristics
of glassy polymers [20]. This results in rendering of inherent size and shape selectivity
as well as mechanical stability. Hence, glassy polymers have found to be more promising
for industrial gas separation applications [26].
One of the key measures in development of gas separation membranes is the
“upper bond” or “trade-off” line which has extensively been in use as a measure for
evaluation of the new membranes. This concept was emerged by Robeson [38] and
indicated that polymeric materials empirically lie on or below this line. Each gas pair has
its own specific trade-off line and for instance, the trade-off line for oxygen/nitrogen
separation is illustrated in Figure 1.2. New developments in membrane materials are
targeted for the upper part of this line which indicates the high permeability and
selectivity performance. It is interesting to note that despite the emergence of numerous
polymers in the past years, only about a handful of materials have been utilized in the
industrial scale. The primary choices include polycarbonates, polysulfones, polyesters,
polypyrrolones, and polyimides which the latter constitutes the largest family of polymers
for this application.
Besides to polymeric materials which have been widely in use for many years,
inorganic materials are also receiving attentions owing to their superior separation
properties and a rapid growth in market share for this class of membranes are anticipated
in near future. Inorganic membranes especially molecular sieving materials such as silica,
18
porous glass, crystalline zeolites, microporous beryllium oxide powders and carbon
molecular sieves have been under intensive research studies due to their potential in
surpassing the traditional upper bond of glassy polymers [38,40,41].
Figure 1.2. Trade-off line of oxygen permeability and oxygen/nitrogen selectivity [39].
The position of molecular sieving membranes with respect to trade-off line was depicted
in previous figure. Although among all, zeolites and carbon molecular sieves have
attracted more attentions in development of high performance membranes, nevertheless,
their high production cost, fragility and reproducibility are the main obstacles for large
scale applications.
19
Among the versatile polymeric material, polyimides are a class of organic resins
which exhibit outstanding engineering properties, especially thermal stability. Their
introduction in the 1960s made significant contributions to meet exacting demands of
industry, aerospace, military and nuclear developments. Although polyimide resin
structures were known some years earlier, the commercial developments by DuPont led
in 1961 to the introduction of film (under the tradename of Kapton) and varnishes for
electrical applications. Subsequently moulding powders, laminating resins, foams and
composite materials and especially high performance adhesives became available.
Generally polyimide materials due to their peculiar properties have become
important and are extensively used in variety of technological applications, such as
semiconductor devices, high-temperature adhesives and high-performance composite
materials. Polyimides have exceptional heat resistance, where very high-level mechanical
properties can be sustained at temperatures of 250°C or more. Excellent electrical,
solvent resistance, flame retardance, abrasion resistance, oxidative and radiation
resistance properties have led to a range of critical applications. The possible replacement
of some metal and ceramic components shows the extraordinary advances made in the
developments of organic plastics within a short time span. Industries such as nuclear,
aerospace, electronics, automotive, etc., as well as products such as self-lubricating
pumps, bearings and such, indicate the true value and penetration of polyimides from
exotic engineering areas to those of everyday life.
20
1.3.2 Membrane Design and Structures
1.3.2.1 Dense Versus Porous Membranes
Membranes, according to their structural characteristics, can be divided into two
general categories of dense and porous which can have significant impacts on their
performance as separators and/or reactors. Dense membranes are free from discrete or
well-defined pores or voids. The difference between the two types can conveniently be
determined by the presence of any pore structure under electron microscopy. The
effectiveness of a dense membrane strongly depends on the intrinsic properties of the
material, the species to be separated and their interaction with the membrane. The
microstructure of a porous membrane can vary according to the method of preparation.
Those membranes that possess essentially straight pores across the membrane thickness
are referred to as straight pore or nearly straight pore membranes. The majorities of
porous membranes, however, have interconnected pores with tortuous paths and are
called tortuous pore membranes.
1.3.2.2 Symmetric Versus Asymmetric Membranes
When the separating layer and the bulk support designed for mechanical strength
are indistinguishable and show an integrally homogenous structure and composition in
the direction of the membrane thickness, it is called a symmetric or isotropic membrane.
Since the flow rate through the membrane thickness is inversely proportional to the
membrane thickness, it is very desirable to make the homogenous membrane layer as thin
as possible. However, very thin stand-alone membranes typically do not exhibit
mechanical integrity to withstand the usual handling procedures and processing pressure
21
gradients found in many separation applications. A practical solution to the dilemma has
been the concept of an asymmetric or composite membrane where the thin separating
layer and the open-cell mechanical support structures are distinctly different
[42,43,44,45]. In this anisotropic arrangement, separation of the species in the feed
stream and ideally the majority of the flow resistance (or pressure drop) also take place
primarily in the thin separating layer. The underlying support layer should be
mechanically strong and highly porous that prevent from any considerable contribution to
the transport resistance of the penetrants across the membrane.
A membrane is called asymmetric, if it has a graded pore structure made on the
processing step and frequently from the same material across its thickness. On the other
hand, the membrane is called asymmetric composite, if it is constructed of two or more
distinctively different layers made at different steps. A predominantly thick layer in this
type of membrane provides the necessary mechanical strength to other layers and is
called the support layer or bulk support. Asymmetric composite membranes have the
advantage that the separating layer and the support layer(s) can be tailored with different
materials. Permselectivity and permeability properties of the membrane material are
critically important for the separating layer, while the material of the support layer(s) is
chosen based on its mechanical strength and other considerations such as chemical
resistance. Ideally, the interface between the two layers and the bulk structure of the
support layer must be porous in order to have a minimal gas transport resistance. In
addition, the two layers must be delaimination-free at the interface.
22
Asymmetric composite membranes can have more than two layers in which the
separating layer is superimposed on more than one support layer. In this case, the
intermediate layer serves as a major purpose of regulating the pressure drops across the
membrane by preventing any appreciable penetration of the very fine constituent particles
into the pores of the underlying support layer(s). Typically the intermediate support layer
is also thin. Figure 1.3 illustrates the structural difference among symmetric and
asymmetric membranes.
Figure 1.3. Typical membrane morphologies [45]
Another promising development on asymmetric membranes worthy of mentioning
is dual-layer hollow fiber membranes. Compared to flat membranes, hollow fiber is more
favored configuration due to the following advantages: 1) large membrane area per
volume unit; 2) high gas flux (i.e., high productivity); and 3) good flexibility and easy
23
handling in the module fabrication. Although high performance polymeric materials have
been synthesized recently with the development of material chemistry, it is not
economically attractive due to high price if these materials are applied for the entire
single-layer hollow fibers. Therefore, dual-layer hollow fiber membranes made by a co-
extrusion technology could be a potential solution. Therefore, fabrication of hollow fibers
in the form of dual-layer can bring considerable cost and time savings.
1.3.2.3 Dynamic in-situ Membranes
There is a type of inorganic membranes that are formed in-situ in the application
environment. They are called dynamic membranes which have been studied in a great
deal especially during the 1960s and 1970s. The general concept is to filter a dispersion
containing the suspended inorganic or polymeric colloids through a microporous support
to form a layer of the colloids on the surface of the support. This layer becomes the active
separating layer (membrane).
Over time, this permselective layer is eroded or dissolved and must be replenished
as they are washed away in the retentate. Commonly used materials for the support are
porous stainless steel, carbon or ceramics. Dynamic membranes have been studied for
reverse osmosis applications such as desalination of brackish water, but found to be
difficult to provide consistent performance and the added cost of the consumables makes
the process unattractive economically. Therefore, only limited applications for recovering
polyvinyl alcohol in the field of textile dyeing is commercially practiced.
24
1.3.2.4 Liquid Membranes
There is another type of membrane called liquid membrane where a liquid
complexing or carrier agent supported or immobilized in a rigid solid porous structure
function as the separating transport medium [46,47,48]. The liquid carrier agent
completely occupies the pores of the support matrix and reacts with the permeating
component on the feed side. The complex formed diffuses across the membrane/support
structure and then releases the permeate on the product side and at the same time recovers
the carrier agent which diffuses back to the feed side. Thus permselectivity is
accomplished through the combination of complexing reactions and diffusion.
There is often known as facilitated transport which can be used for gas separation
or coupled transport or separation of metal compounds through ion transport. An example
of the former is some molten salts supported in porous ceramic substrate that are selective
toward oxygen and of the latter is some liquid ion exchange reagent for selectively
transporting copper ions. In this configuration, the composite for the liquid membrane
and its support can be considered to be a special case of dense membranes. Despite their
potential for very high selectivity liquid membranes suffer from physical instability and
are not likely to be a major commercial force in the separation industry.
1.3.3 Membrane Module Configurations
Membrane gas separation system offers great benefit that enables it to be applied
in various industrial processes. Principally, the membrane module is the heart of a
membrane system to determine the yield and efficiency of a separation process. Industrial
25
membrane modules are regularly based on both flat and hollow fiber configurations. The
vast majority of industrial membrane modules are constructed into five basic designs:
plate-and-frame, spiral wound, hollow fiber, tubular and capillary. Flat sheet membranes
are usually contained in the plate-and-frame devices and spiral wound elements, whereas
the modules of hollow fiber, tubular and capillary involve the hollow fiber configuration.
Three most general modules employed in industrial membrane separation processes will
be discussed.
1.3.3.1 Plate-and-Frame Membranes
Plate-and-frame design replicates conventional filtration setup. It is conceptually
simple, which consists of a package of flat sheet membranes. Plate-and-frame modules
are easy to fabricate and the area of membranes are well defined. The flat sheet
membranes, mainly used for experimental purpose to characterize the intrinsic properties
of membrane are stacked together like a multilayer sandwich in a frame. This module
consists of a cylindrical tube, spacer material to separate the membrane envelopes and
rubber gaskets to direct the flow through the module and seal the assembly [44]. The
plate-and-frame package design is illustrated in Figure 1.4. Lowest surface area/unit
separator volume (~100-400m2/m3) is the major drawback of plate-and-frame module.
Consequently, this module configuration is not favorable for gas separation application
and relegated to oxygen enrichment for small scale medical application [49].
26
Figure 1.4. Schematic drawing of a plate-and-frame module [44,50]
1.3.3.2 Spiral Wound Modules
The spiral wound module maintains the simplicity of flat membranes fabrication,
but it is the next logical step from a flat membrane. This element increases the packing
density (membrane surface per module volume) remarkably to 300-1000 m2/m3
compared to plate-and-frame modules. As shown in Figure 1.5, the assembly consists of a
sandwich of flat sheet membranes to form an envelope enclosing a separator/spacer in
them to provide mechanical strength and permeate flow space. The membranes envelope
is wound around a central core of a perforated collecting tube. When a spiral wound
27
module is in operation, the feed gas flows outside the membrane envelope and the
permeate is collected inside and removed through the central collector.
Figure 1.5. Spiral wound elements and assembly
1.3.3.3 Hollow Fiber Modules
The hollow fiber module consists of a large number of hollow fibers assembled
together into a pressure vessel. The membranes are thin hollow tubes with a very small
diameter. The geometric arrangement of module is similar to conventional heat-
exchanger assembly, presented in Figure 1.6. It offers a fairly high packing density with a
maximum membrane surface area per unit volume as high as 10,000 m2/m3 [50,51].
Typically the high pressure feed enters either into shell side or bore side and permeate is
collected from the other side. However, the major disadvantage associated with hollow
fibers is significant pressure drops at bore side when large quantities of gas permeating
the membrane. Therefore, for the gas separation, feed stream must be relatively clean
with preferably shell side feeding to avoid high pressure drops and attaining high
membrane area.
28
(Retentate)
(Permeate)
(Feed)
Figure 1.6. Hollow fiber separator assembly [51]
The selection and application of membrane modules are principally depending on
the economic considerations, separation performance and practicability (ease of cleaning,
ease of maintenance, ease of operation, compactness of the system, scale and the
possibility of membrane replacement). Table 1.5 shows the characteristic of a basic
membrane module. According to this Table, spiral wound and hollow fiber modules are
the two major choices for gas separation application. Spiral wound modules tend to have
a lower permeate pressure, whereas hollow fiber modules exhibit the highest packing
density among all the modules. To overcome the problem of pressure drop in hollow
fibers, the compression and recompression of product gas must often be considered but
they usually result in a significant cost addition for a given process. Universally, the need
to achieve high packing density in a cost-effective manner is probably the most critical
criteria to be considered in a membrane system.
29
Table 1.5. Qualitative comparison of various membrane modules [50]
Plate-and- Spiral Hollow

Tubular Frame wound Capillary fiber
Packing density Low Very high
Investment High Low
Fouling tendency Low Very high
Cleaning Good Poor
Membrane replacement Yes/No Yes No No No
1.4 TRANSPORT MECHANISMS IN GAS SEPARATION MEMBRANES
Gas separation by membranes is a straight forward process concept driven by the
pressure gradient imposed between upstream and downstream. Permeation is a rate
controlled process and separation degree is determined by the selectivity of membrane at
the conditions of separation, including pressure, temperature, flow rate, and membrane
area [52]. A membrane will separate gases only if some components pass through the
membrane more rapidly than others. Depending on the pore sizes in membrane matrix,
there are four fundamental transport mechanisms in gas separation membranes, namely
(1) Poiseuille flow, (2) Knudsen diffusion, (3) Molecular sieving and (4) Solution-
diffusion, as illustrated in Figure 1.7.
From this Figure, it is obvious that there are two major types of membranes
involved in the gas separation. The first is a porous membrane in which the gases are
separated on the basis of their molecular size through the small pores in the membrane
matrix, by Poiseuille flow, Knudsen diffusion or Molecular sieving. Nevertheless, the
vast majority of commercial application is based on nonporous membranes (containing
no holes or pores in the conventional sense) through solution-diffusion mechanism.
30
Poiseuille Flow Knudsen Diffusion Molecular Sieving Solution-diffusion
Figure 1.7. Schematics of main mechanisms of membrane-based gas separation
1.4.1 Poiseuille Flow
The Poiseuille flow also known as viscous flow occurs when the mean pore
diameter is larger than the mean free path of the gas penetrants. The mean free path here
refers to the average distance traversed by a gas molecule between collisions and it is
pressure and temperature dependent. In this condition, membrane contains pores larger
enough to allow convective flow, where gas molecules collide exclusively with each
other and no separation is obtained between the gas components. This type of transport
mechanism is observed for the membranes having the much larger pore sizes than gas
molecules, at pore size, d p >10µm and the flux is proportional to r4.
1.4.2 Knudsen Diffusion
Convective flow will be replaced by Knudsen diffusion in a porous membrane
whose pore sizes are less than the mean free path of the gas molecules [42]. Gas
31
molecules therefore interact with pore walls much more frequently than with one another
and allow lighter molecules to preferentially diffuse through pores to achieve separation.
Knudsen diffusion principally takes place in the membranes with the pore size of 50-100
Å in diameter [27].
Knudsen diffusion is achieved when permeating species flow via the membrane
almost independent of one another. Hence, the Knudsen diffusion coefficient, D k (m2.s-1)
is independent of pressure. For an equimolar feed the permeation rate of Knudsen
diffusion is inversely proportional to the square root of the molecular weight of the
different compounds in the following equation [53]:
𝐷𝐷𝑘𝑘 = 0.667𝑟𝑟𝑟𝑟 = 97𝑟𝑟�𝑀𝑀𝑇𝑇𝑤𝑤 (1.1)
where the average pore radius is given by r (m), υ is the average molecular velocity (m.s-
1
) and T is the operating temperature. Whilst the highest attainable separation factor
between two different gas molecules i and j equals to the square root of the ratio of the
molecular weights of the species, as shown in equation (1.2).
𝑀𝑀
𝛼𝛼𝑖𝑖𝑖𝑖 = � 𝑀𝑀𝑤𝑤𝑤𝑤 (1.2)
𝑤𝑤𝑤𝑤
Consequently, such membranes are not commercially attractive in general for standard
application due to their relatively low selectivity.
1.4.3 Molecular Diffusion
Molecular sieving separation is primarily based on the precise size discrimination
between the gas molecules through the ultramicropores (<7Å in diameter). Molecular
32
sieving membranes become increasingly important in the gas separation especially for
inorganic membranes due to their reported higher productivity and selectivity than
solution-diffusion polymeric membranes [54,55]. Their porous nature has led to high
permeability, while the high selectivity is achieved through effective size and shape
exclusion between the gas species. This happens when the pore diameters are small
enough to allow the permeation of smaller molecules while obstructing the larger
molecules to diffusive through. Even if both molecules enter the pores; the larger one
would experience stronger repulsive forces. This energetically biased selectivity is called
“energetic selectivity”. It is also believed that the more subtle contribution to selectivity
is from “entropic selectivity” [56], in which the rotational freedom of one component is
restricted to a higher degree than that of the other components.
Carbon molecular sieve membranes (CMSMs) and zeolites are the typically
membranes dominated by molecular sieving mechanism and give the high separation
performance. The ratio of the gas molecular size to the micropore diameter controls the
gas permeation rate and separation in molecular sieving materials [57]. For example,
zeolite 4A with a pore size of 3.8 Å has an O 2 /N 2 selectivity of approximately 37 at 35oC
[58].The ideal selectivity of carbon molecular sieve membranes for CO 2 /CH 4 separation
has been reported to be as high as 200 [59]. The pore size of zeolite maybe controlled or
modified by choosing suitable synthesis, de-almunation, and ion-exchange [60]; as for
CMSMs, the pore size can be controlled by choosing polymer precursor, pyrolysis
conditions, pretreatment and post treatment [61].
33
1.4.4 Solution–diffusion Model
The solution–diffusion mechanism is widely employed for explaining gas
transport through dense polymeric membranes [62]. Based on this model, the gas
permeability (P) across the membrane is a product of solubility (S) and diffusivity (D).
P = S×D (1.3)
The ideal gas pair (A/B) permselectivity comprises the solubility (S A/S B ) and diffusivity
(D A /D B ) selectivities, which should complement each other for optimal separation factor.
PA  S A   DA 
α AB = =  ×  (1.4)
PB  S B   DB 
The gas solubility of polymeric membranes is dependent on the (1) condensability of the
penetrant gases, (2) nature of interactions between the polymer and the penetrants and (3)
chain packing density in glassy polymers [63]. For natural gas separation, the solubility
of CO 2 is higher than CH 4 due to the significant difference in the condensability of the
gases (T c, CO2 = 304 K and T c ,CH4 = 191 K). On the other hand, since the gas diffusivity
mainly depends on the kinetic diameter (d KT ) of the penetrants, the diffusivity of CO 2 is
expected to be larger than CH 4 (d KT,CO2 = 3.3Ǻ and d KT,CH4 = 3.8Ǻ) [64]. This explains
the preferential permeation of CO 2, relative to CH 4 for most glassy polymeric
membranes.
1.4.5 Gas Sorption and Diffusion in Glassy Polymers
Several models have been established to explain the sorption of gas molecules in
glassy polymeric membranes but the use of a model based on the dual-mode sorption
theory has been more prevalent [65]. The dual-mode sorption model (Eq. (1.5)) suggests
the presence of Henry and Langmuir sorption sites in glassy polymers [31,32,33]. The
34
solubility coefficient is the ratio of total penetrant concentration to pressure, given by Eq.
(1.6).
C ' H bp
C = CD + CH = k D p + (1.5)
1 + bp
C c' b
S= = kD + H (1.6)
p 1 + bp
C is the total gas concentration, p is the pressure and k D represents the Henry law
constant. C D and C H are the gas concentrations at the Henry and Langmuir sites,
respectively. C’ H is the Langmuir capacity constant which varies with polymer type and
structure. b is associated with the affinity of the gas molecules to the Langmuir sites.
Paul and Koros proposed the dual-mobility model to account for the difference in
inherent gas diffusion of the Langmuir and Henry sites [67,68,69]. This model is
presented by equation 1.5 where D D and D H are the diffusion coefficients in the Henry
and Langmuir sites, respectively. F is the ratio of D H to D D and K is (c’ H b/k D ). p 2 is the
pressure at the upstream boundary.
 FK 
P = k D 1 +  DD (1.7)
 1 + bp 2 
From a classical approach, the gas diffusion coefficient, D can be expressed in the form
of an Arrhenius equation shown by equation 1.8.
 − ED 
D = D0 exp  (1.8)
 RT 
Here, D 0 is the pre-exponential factor, R is the gas constant, T is the temperature in
Kelvin and E D is the activation energy for diffusion. Based on another model proposed
35
by Brandt, E D is related to polymer dependent parameters c and f as well as the kinetic
diameter (d) of the gas penetrant which is presented in equation 1.9 [70].
E D = cd 2 − f (1.9)
According to this model, polymers that have high diffusivity selectivity should have high
values of c, which implies high polymer chain stiffness. The term f / c is related to the
average distance between polymer chains.
1.4.6 Free Volume in Glassy Polymers
The presence of free volume in polymers is attributed to the non-equilibrium state
of the polymeric matrix induced by the limited mobility and long relaxation times of
entangled polymer chains [71,72]. For polyimides with flexible backbones, the formation
of irregular voids is due to the minimum barriers of each rotational bonds occurring at
irregular intervals [73,74]. The way in which the gas molecules transverse across the
membranes is described by a series of diffusional jumps through the temporary channels
created by the constantly vibrating polymer chains as shown in Figure 1.8. Therefore, the
size and distribution of free volume, polymer chain mobility and penetrant size govern
the overall gas transport. The free volume entities of polymers are frequently expressed
by the fractional free volume (FFV) [75,76,77,78,79]. The FFV model provides a rough
estimate for gas transport in polymeric membrane but fails to account completely for
experimentally determined results, especially for highly condensable gases [80]. The
discrepancy in the physical interpretation of the parameters in the FFV model created
additional problem for the general acceptance of this model [80,81].
36
1
A
1
B 4 4
1
5 5
1
1 C
2 B
A 2
C
3
3
Position of molecules at one instant Position of molecules at the next instant
Figure 1.8. Motion of gas molecules within the cavities through a series of
diffusional jumps
Free volume elements are characterized by the wide angle x-ray diffraction
(WAXD), which provides the average d-spacing of polymers [81]. Recent investigations
using molecular modelling reveals that the d-spaces are better reflected by the x-ray
scattering associated with 2θ values between 20o and 28o [73]. In a recent work by Miyata
et al., the correlation between the dielectric constant of polyimide and FFV was
established [82]. The positron annihilation lifetime spectroscopy (PALS) is also
employed for free volume analysis [83-87]. A correlation between the measured lifetime
of orthopositronium (o-Ps) and the size of the void volume is used to determine the
average hole size. The reported cavity radii of polyimide free volume usually fall in the
range of 2.5 to 4.5 Ǻ [ 79,86-88] which are comparable to d-spaces measured by WAXD.
These analytical techniques provide valuable information which can be utilized for
optimizing the gas separation performance of polyimide membranes. However, the
characterization is not conducted in-situ and thus, the results are not truly reflective of the
37
actual operating conditions. It should be noted that the interactions between the polymer
chains and the gas molecules affects the chain mobility and the free volume of the
polymeric membranes. Therefore, novel analytical methods capable of examining
polymeric membranes that are subjected to a certain gas pressure are necessary. In
addition, characterization techniques with higher sensitivity and accuracy, simpler
operating procedures and lower costs are required.
1.5 RESEARCH OBJECTIVES AND ORGANIZATION OF DISSERTATION
This research study comprised of four main aspects including the development of
new nanocomposite membranes by using MgO nanoparticles with enhanced gas
separation performance, fabrication of membranes with interpenetration networks from
miscible polymeric blends for hydrogen separation and purification, production of carbon
molecular sieving membranes with enhanced performance for diverse gas separation
applications and fabrication of dual-layer hollow fiber membranes for gas separation in
the semi-industrial scale.
The key impetus for this research is underachievement of conventional polymeric
membranes in surpassing the trade-off between productivity and selectivity. The main
objective of this research is to identify, explore and develop viable techniques in order to
address this challenge and provide membranes with enhanced gas separation
performance. In every aspect of this research study the effect of various variables of
interests will be discussed. For the nanocomposite membranes, the effect of incorporation
38
of nanoscale magnesium oxide particles at different loading was examined. Number of
post-treatment approaches was employed in order to optimize the separation performance
of the membranes. On the other hand, blending technology was exploited for fabrication
of polymeric and carbon molecular sieve membranes. The properties of these membranes
were finely tuned through proper adjustment of parameters and application of suitable
modification techniques. The potentials of polymeric blend membranes were further
extended by fabrication in form of hollow fiber membranes. In order to achieve the above
objectives, the scopes of this study are drawn as follows:
1. Development of new nanocomposite membranes by using MgO nanoparticles
with enhanced gas separation performance
2. Fabrication of membranes with interpenetration networks from miscible
polymeric blends for hydrogen separation and purification
3. Production of carbon molecular sieving membranes with enhanced
performance for diverse gas separation applications
4. Fabrication of novel dual-layer hollow fiber membranes from polymeric blends
for gas separation
This dissertation is organized and structured into seven chapters. Chapter One is
an introductory chapter of this dissertation. It gives an introduction to gas separation
membranes, encompassing the historical development of membranes, industrial
applications and principles of gas separation membrane technology. The discussion
includes membrane materials, structure and design of membranes and membrane module
configurations. In addition, the governing transport mechanisms in gas separation
39
membranes are described. The research objective and outline of this dissertation are also
presented in this chapter.
The information of strategies and approaches in development of membranes for
gas separation are given in Chapter Two. This chapter begins with the description of the
key limitations of existing polymeric membranes. Approaches for molecular design and
tailoring the properties of membranes materials are introduced. Various key modification
techniques including polymer blending, hybridation, thermal annealing, grafting and
halogentaion of polymer backbone and chemical cross-linking are reviewed. Finally, the
current and future developments in each area are presented.
Chapter Three describes the development of gas separation membranes with
enhanced performance by introduction of nanosize magnesium oxide particles followed
by treatment with silver ions. The effects of particle loading on the gas permeability and
separation performance of the membranes are investigated. It is shown that the highest
permeability was observed for the membranes containing 40 wt% MgO loading but with
diminished selectivity compared to the neat Matrimid membrane. The effect of applying
various modification techniques including heat treatment at various temperatures and also
silver ion treatment on the structural and transport properties of the membranes are
discussed.
Chapter Four demonstrates the successful implications of blending technique cum
chemical modification for the fabrication of high performance polymeric membranes for
40
gas separation applications. The effect of variation in composition on miscibility and
microstructure, gas permeability and selectivity of blend membranes is investigated. The
results of the analysis of the microstructure of membranes in terms of their chain packing
density, d-spacing and segmental mobility of polymer chains are provided. Separation
performance of membranes is further ameliorated through chemical modification of blend
constituents. The results indicate that higher tendency of Matrimid toward cross-linking
reaction contributes more in controlling the transport properties of membranes through
diffusion coefficient by increase in chain packing density and diminishing the excess free
volumes. The promising features of developed membranes for various gas separation
applications are presented.
Chapter Five introduces the development of membranes composed of
poly(benzimidazole) (PBI) and various polyimides and the study regarding to their
capabilities in formation of homogenous blends with satisfactory morphology for
fabrication carbon molecular sieve membranes. Attempts are made to unravel the
correlations between the pyrolysis process parameters and separation performance of
developed membranes. Modification of precursors by chemical cross-linking prior to
carbonization and its effects on the separation performance of the membranes is
discussed. This research study accentuates the necessity and importance of adopting a
proper strategy in exploiting synergistic beneficial features of advanced materials (PBI),
technology (polymer blending), process (carbonization) and modification techniques
(cross-linking) toward achieving membranes with desired performance.
41
Chapter Six introduces the development of novel high performance gas separation
membranes through integrating of the concepts of polymer blending and dual-layer
hollow fiber spinning process. Attempts are made to unravel the effect of various key
parameters on the morphological evolution, transport properties and separation
performance of the fabricated hollow fiber. The effects of various parameters such as air
gap distance, application of elongational drawing, outer dope flow on the gas permeance
and selectivity of the membranes are discussed. Silicone rubber coating and chemical
modification are used as potential tools for modification of the membranes and tuning
their gas transport and separation performance.
The general experimental approaches and methodologies, along with the materials
involved are provided in their respective research study. This includes the details of
membrane preparation, characterization, modification, treatment and other miscellaneous
tests.
General conclusions drawn from this research study are summarized in Chapter
Seven. Inclusive in this final chapter are some recommendations and suggestions for
future research related to this work.
42
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51
CHAPTER TWO
STRATEGIES AND APPROACHES IN DEVELOPMENT OF GAS
SEPARATION MEMBRANES
The worldwide demand for the use of natural gas as a cleaner and more efficient
fuel is constantly rising. In addition, natural gas (methane) is considered as a principle
feedstock for the chemical industry. The global consumption of natural gas is projected to
increase from 95 trillion cubic feet in 2003 to 182 trillion cubic feet in 2030 [1]. Since
raw natural gas from various origins is different in composition, the potential growth in
the demand for methane implies the need for separation technologies with outstanding
efficacy. Although methane constitutes the key component of natural gas, it may also
contain considerable amounts of impurities including water, carbon dioxide, nitrogen,
hydrogen sulfide and other hydrocarbons. One of the major steps in natural gas treatment
involves the removal of acid gases (CO 2 and H 2 S) before it is delivered to the pipelines
or stored into portable cylinders as compressed natural gas. The necessity for natural gas
sweetening is to (1) increase the fuel heating value, (2) decrease the volume of gas to be
transported in pipelines and cylinders, (3) reduce pipeline corrosion within the gas
distribution network and (4) prevent atmospheric pollution [2].
Currently, natural gas treatment is one of the principal industrial gas separation
processes and the market for new purification systems may exceed $5 billion per year [3].
52
Absorption of acid gases in basic solvents (such as amine or hot aqueous potassium
carbonate solutions), pressure swing adsorption and membrane technology are examples
of natural gas purification technologies [4]. Despite the full maturity of the gas absorption
processes, they basically suffer fromthe need for solvent regeneration process, difficulty
to be justified for small gas fields, large footprint for offshore applications and lack of
robustness against fluctuations of feed composition. Similarly, pressure swing adsorption
(PSA) is highly capital intensive and requires significant energy consumption. In
comparison, the advantages of membrane technology include potentially higher energy
efficiency, ease of scale-up, better utilization of space and environmentally friendly [5].
In particular, from the economic point of view, membrane technology may appear more
advantageous for small-to-medium scale separations and non-stringent product purity
requirements. It is worthwhile to note that the current trend is the development of hybrid
membrane/absorption processes capable of eliminating both CO 2 and H 2 S impurities
from natural gas [6]. This is due to the fact that membrane separation technology alone is
not yet well proven for H 2 S removal [7].
The gas transport through membranes has been studied since the 1950s but the
immaturity of the fabrication technology to produce high flux membranes has retarded
their use in industry. The application of membrane technology for CO 2 removal from
natural gas emerged in the 1980s after several major breakthroughs. One of the principal
revolutions was the preparation of high flux asymmetric Loeb-Sourirajan membranes
with selective layer thicknesses of less than 0.1µm [8]. However, the formation of defects
during membrane fabrication restrained the direct application of these membranes for gas
53
separations. Henis and Tripodi’s invention of applying a thin layer of silicone rubber
coating on the membrane surface provided a solution to overcome this limitation [9]. The
emergence of new module designs like spiral-wound and hollow fibers led to the
fabrication of smaller membrane configurations with higher surface-to-volume ratios
[10].
In addition to the fabrication methods and module designs, works have also been
in progress to develop membrane materials with enhanced properties and separation
performance in process environments [11]. For membranebased natural gas purification,
it is highly desirable to explore materials which can selectively remove CO 2 from the
mixtures, thereby maintaining CH 4 at or near feed pressure and avoiding costly gas
recompression. There are many criteria for the selection of membrane materials and the
most important ones are high gas permeation flux and gas pair selectivity [8]. Other
factors may include the mechanical and thermal stability, manufacturing reproducibility,
tolerance to contaminants and economical aspects. A number of reviews examining the
various materials for gas separation membranes have been published over the last two
decades [3,6,8,12–19]. Among the studied materials, it was noted that polyimides (PI)
which exhibit high permselectivity for various gas pairs (e.g. CO 2 /CH 4 and O 2 /N 2 ), high
chemical resistance, thermal stability and mechanical strength have attracted much
attention. This is well supported by the significant increase in the number of publications
related to polyimide membranes over the years. Du Pont Co. (USA) and Ube Industries
(Japan) have been pioneers in the commercial application of polyimides in separation
processes [21]. The industrial application of polyimide membranes by DuPont began in
54
1962 with separation of helium from natural gas which was subsequently applied to the
separation of CO 2 from various gas streams.
In view of the potential use of polyimides as materials for fabricating high
performance gas separation membranes, an understanding of the physical and chemical
properties in relation to the gas separation performance must be established. This is due
to the fact that the intrinsic gas transport properties of polyimide membranes have been
found to be linked to their chemical structures. The interdependencies have been well
summarized in several articles [22-27]. Specific tailoring of the polyimide molecular
structure can be regarded as a viable approach in obtaining the desired gas separation
properties of the resultant membranes. Alternatively, exploration of modification
techniques may open up additional opportunities for better exploitation of the existing
polyimides.
2.1 KEY LIMITATIONS OF EXISTING POLYMERIC MEMBRANES
2.1.1 Permeability Versus Permselectivitiy
It is desirable to obtain gas separation membranes with both high permeability
and permselectivity. In the early 90s, Robeson gathered the permeability and
permselectivity data for various binary gas pairs from the literature and discovered the
existence of upper bound curves indicating a general tradeoff between permeability and
permselectivity [28]. The empirical correlation of the Robeson upper bound is
represented by equation 2.1.
55
ln α AB = ln β AB − λ AB ln PA (2.1)
In a subsequent study by Freeman, a more comprehensive physical interpretation of the
upper bound was conducted and the proposed correlation is given by equation 2.2 [29].
For glassy polymers, a and b are constants equal to 0.64 and 11.5 cm2/s, respectively and
f is a polymer dependent parameter [30-31].
 d  2    S   d  2  
1 − a 
ln α AB = −   − 1 ln PA + ln A  −  B  − 1 b −
B
f 
 − ln S A (2.2)
 d A     S B   d A    RT   
A comparison of equations 2.1 and 2.2 indicates that the slope of the upper bound, λ AB is
dependent only on the gas kinetic diameters (d A and d B ) while the intercept of the upper
bound is a strong function of the nature of the gaseous penetrants and the polymer.
Hence, for a given gas pair, the slope of the upper bound remains constant. This implies
that a performance surpassing the upper bound is achievable by placing greater emphasis
on increasing the solubility selectivity, inter-chain spacing and chain stiffness. Recently,
Robeson utilized a larger data set than before to re-examine the upper bound [32].
Despite the continuous efforts to develop novel membrane materials, the upper bound
line for CO 2 /CH 4 exhibited only minor shifts [32]. For our current study, a thorough
literature survey was conducted to obtain the CO 2 /CH 4 separation performance of
aromatic polyimide membranes. The collected data are summarized and compared with
the upper bound in Figure 2.1. It is evident that only a minority of the aromatic
polyimides fall close to or above the trade-off line.
56
1000
Present upper bound (2008)

CO2/CH4 permselectivity
Prior upper bound (1991)

100
10
1
0.1 1 10 100 1000
CO2 permeability
Figure 2.1. Robeson’s tradeoff curve for CO 2 /CH 4 gas pair
2.1.2 CO 2 - Induced Plasticization and Conditioning
Penetrant-induced plasticization and conditioning are two aspects which need to
be considered in the fabrication of high performance glassy polymeric membranes. These
phenomena are found to be more severe in natural gas separation which involves highly
condensable gases (e.g. CO 2 , H 2 S, H 2 O) and other heavy hydrocarbons [33,34-40].
These undesirable effects are present in polyimide membranes, despite their good
chemical integrity compared to other polymers. In the following discussion, the gist of
plasticization and conditioning are presented to better understand their impacts on the
separation performance of polyimide membranes for natural gas purification.
57
Plasticization is a repertoire of pressure dependent phenomena caused by the
dissolution of certain components within the polymer matrix which disrupts chain
packing and enhances inter-segmental mobility [33,34]. At relatively low CO 2 pressures,
the gas permeability of a polyimide membrane decreases with increasing pressure. This
behavior is attributed to the gradual saturation of microvoids in the membrane (i.e.
reduced solubility coefficient) which in turn reduces the permeability. Further increase in
pressure results in an upward inflection in gas permeability. The pressure at which the
corresponding gas permeability exhibits a minimum is known as the plasticization
pressure (P plas). The pressure-permeability relationship is inadequate for determining the
incipient point of plasticization since the phenomenon occurs considerably below P plas
[41]. Therefore, another diagnosis to determine the beginning of plasticization involves
examining the absolute heat of sorption as a function of pressure. The onset of
plasticization corresponds to the point at which the change in the heat of sorption with
pressure transforms from a negative value to a positive one [41].
For CO 2 /CH 4 separation using glassy polymeric membranes, CO 2 -induced
plasticization accelerates the permeation of methane, thus deteriorating the CO 2 /CH 4
permselectivity. CO 2 -induced plasticization leads to pressure, temperature, time and
thickness dependence in the gas transport properties of glassy polymeric membranes [41,
42-47]. The temperature dependence of CO 2 -induced plasticization is investigated by
Duthie et al [47]. The variations in CO 2 permeability as a function of CO 2 fugacity at
different operating temperatures reveal that the plasticization phenomenon is more
pronounced at lower temperatures [47]. Plasticization results in non-constant CO 2
58
permeability. For example, the relative increase in the gas permeability of 6FDA-MDA
film is larger than 40% after the lapse of several hours and it does not reach a steady-state
value within the experimentation time [45]. The thickness-dependence of CO 2 -induced
plasticization was clearly illustrated using 6FDA-durene polyimide in a study by Zhou et
al [46]. An accelerated plasticization behavior is observed in ultra-thin dense polyimide
films, attributed to the weak micro-mechanical properties and severe swelling effects
caused by CO 2 .
Another phenomenon closely associated with CO 2 -induced plasticization is the
effects of conditioning. Conditioning is related to the alterations in the properties of
glassy polymers upon exposure to highly soluble gases [48]. CO 2 sorption in polymer can
severely and in most cases permanently change the morphology and transport properties
of the membrane even after the gas molecules are fully desorbed [48]. The resultant
conditioned membranes exhibit irreversible volume dilation and new steady-state gas
transport properties. CO 2 conditioning leads to simultaneous increment in gas diffusivity
and solubility which is dependent on the extent of volume expansion. Polyimides show
significant volume dilation and increment in gas permeability [42]. Since the effects of
CO 2 -induced plasticization and conditioning significantly deteriorate the separation
performance of polyimide membranes, any effort toward its suppression or even
elimination would have great beneficial impacts.
2.1.3 Physical Aging
59
It is well demonstrated that the non-equilibrium state of glassy polymers is mainly
due to the thermal cooling process across the glass transition temperature [49-51]. Hence,
there is a tendency for polymeric chains to undergo “physical aging” which is a gradual
molecular rearrangement process toward attaining an equilibrium state. One consequence
of aging is the densification of the polymer matrix with a corresponding decrease in the
free volume. There abound several numbers of research studies and publications on this
subject of aging.
Two mechanisms have been proposed to account for the collapse of free volume
during the physical aging process. Alfrey proposed that some of the free volumes in the
membrane structure exist temporarily and can be lost in the course of time via diffusion
toward the membrane surface [52]. This phenomenon is shown in Figure 2.2. It should be
highlighted that the rate of free volume diffusion is a function of membrane thickness; it
occurs in an accelerated pace for thinner membranes [48,50, 53-54]. Subsequently, Curro
and co-workers and Hirai and Eyring proposed that lattice contraction (Figure 2.2.) also
contributes to the overall reduction in the free volume [55]. Lattice contraction is not
thickness dependent. The rate of aging is strongly associated with the polymer type
[48,53-54,56-59]. For a polymer with poor chain packing efficiency and high FFV
values, the decline in free volume resulting from physical aging is more significant than
that of a polymer with lower FFV. Kim and co-workers investigated the aging
phenomenon in homo- and co-polyimides, and faster aging rate was observed for
polymers with higher free volume [58-59].
60
Time = 0
z
Glassy polymer matrix y

forming the membrane x
Free volume within the Membrane thickness, l

matrix – Langmuir sites
Time > 0
3-dimensional diffusion
of free volume from the
interior to the surface
For simplicity, only Lattice
diffusion in the z contraction
direction is shown in the radial
direction
Time >>> 0
Reduction in free volume

and densification of the Reduction in membrane
polymer matrix thickness, l - Δl
Figure 2.2. Diffusion of free volume and lattice contraction (physical aging).
One critical consequence caused by physical aging is that the gas separation
performance of these glassy polymeric membranes becomes time dependent. As the
aging time increases, the decrease in free volume reduces the gas permeability and
possibly a corresponding increase in gas pair permselectivity. This introduces uncertainty
in the gas separation performance in the long run which acts as a barrier to the
commercialization of polyimide membranes for industrial gas separation. Therefore,
overcoming the problem of physical aging in polyimide membranes represents a big
challenge for membrane researchers.
61
2.2 MOLECULAR DESIGN OF POLYMERIC MEMBRANES FOR GAS
SEPARATION
Polyimides exhibit excellent gas separation performance and good
physiochemical properties. Therefore, polyimide membranes have been extensively
explored for their potential applications in natural gas purification. Molecular tailoring of
polyimides is one approach that is utilized in the search for better membrane materials for
CO 2 /CH 4 separation. The molecular design of polyimides can be broadly classified into
two categories. The first encompasses purely polyimide system whereby the chemical
constituents and configurations of the dianhydrides and/or diamines used for polyimide
synthesis are varied in a systematic manner. The other category is the chemical fusion
(copolymerization) of polyimides with polymers from other classes.
2.2.1 Tailoring Pure Polyimide Systems
Numerous dianhydrides and diamines are available and their combinations give
rise to various polyimides which have the potential for use in natural gas separation.
Among them, aromatic polyimides containing hexafluoroisopropylidene-diphthalic
anhydride (6FDA) are of particular interest [60-63]. The CF 3 groups in 6FDA
considerably increase chain stiffness on the basis of steric bulk hindrances and effectively
reduce chain packing. Moreover, 6FDA-based polyimides exhibit good balance between
high CO 2 permeability and CO 2 /CH 4 selectivity [60-63]. In view of the advantages of
6FDA-based polyimides, this section aims to provide further insights on the relationship
between their polymer structure and the membrane separation performance. The general
62
structure of a polyimide is shown in Figure 2.3., where R 1 and R 2 refer to the dianhydride
and diamine moieties, respectively. Generally, polymer chain rigidity determines the
permselectivity while inter-chain spacing and chain mobility governs the permeability. In
the molecular design of polyimides, the main factors affecting the gas transport properties
are (1) spatial linkage configurations, (2) type of bridging groups, and (3) bulkiness and
polarity of pendant groups constituting the polymer.
O O
C C
N R1 N R2
C C
O O
Figure 2.3. General chemical structure of polyimide
For spatial linkage configurations, unsymmetric meta-linked polymers exhibit
better chain packing efficiency and restricted rotational freedom compared to their
symmetric para-linked isomers [64-68]. Therefore, the meta-isomers show lower FFV
and gas permeability but higher gas pair selectivity [64-66]. A comparison of 6FDA-
based polyimides containing different types of linkages is presented in Table 2.1. [64-66].
63
Table 2.1. Effect of meta or para linkages on gas separation performance (6FDA-based)
PCO 2 S CO 2 DCO 2
PCO 2 S CO 2 DCO 2
Name and chemical structure of diamine PCH 4 S CH 4 DCH 4 FFV Ref.
4,4’ – oxydianiline (4,4’ODA) 16.7 4.1 3.1 49 3.4 14 0.165 [64]
3,4’ – oxydianiline (3,4’ODA) 6.11 3.5 1.3 49 4.3 14 0.162 [64]

O
2,2-bis(4-aminophenyl)hexafluoropropane (6FpDA) 63.9 4.7 10.3 39.9 3.3 12.2 0.190 [65]
CF3
C
CF3
2,2-bis(3-aminophenyl)hexafluoropropane (6FmDA) 5.1 2.9 1.3 63.8 3.6 17.7 0.175 [65]
CF3
C
CF3
4,4’-diaminodiphenyl sulfone (pDDS) 16 5.6 2.1 47 3.8 12 0.149 [66]

O
S
O
3,3’-diaminodiphenyl sulfone (mDDS) 2.3 4.3 0.4 74 3.8 18 0.146 [66]

O
S
O
Units for P, S and D are barrer (1 barrer = 1 x 10-10 cm3 (STP)-cm/cm2 s cmHg), cm3 (STP)/cm3 atm and 10-8 cm2 /s respectively
64
An exception to the general trend between 6FDA-4,4’ODA and 6FDA-3,4’ODA
polyimides has been observed [64]. Despite the presence of meta linkages, there is no
change in CO 2 /CH 4 selectivity because the effect is diluted by the presence of other para
linkages. A comprehensive discussion on the dilution effect for polysulfones, similarly
applicable to polyimides, has been investigated by Aitken et al [69].
The nature of the bridging groups present in the polymer backbone influences gas
separation performance. Table 2.2. lists several 6FDA-based polyimides with different
bridging groups in the diamine moieties [65-66,70]. Bridging groups with low energy
barriers (e.g. O and S linkages) facilitate chain motions and results in higher gas
permeability while the incorporation of bulky linkage groups (e.g. CH 2 and O=S=O)
lowers gas permeability. With reference to Table 2.2., the order of increasing CO 2 /CH 4
selectivity of the polyimides (PPTI-1 < pDDS < 4,4’ODA) corresponds to the order of
increasing electronegativity of the bridging groups (S < O=S=O < O) [65-66,70]. Higher
electronegativity leads to stronger chain-to-chain interactions and enhanced selectivity.
The presence of bulky pendant groups increases inter-chain spacing and reduces
the packing efficiency of the polymer chains. Due to these bulky appendages (e.g. CH 3 ,
CF 3 and C 2 H 5 ), the FFV and gas permeability increases [64-66]. The effect of substituent
size on the gas separation performance of polyimides is shown in Table 2.3. [64-66]. The
polarity of the substituent groups affects chain-to-chain interactions which subsequently
influences chain rigidity and packing efficiency. With reference to Table 2.4., the greater
polarity of C=O groups in 6FDA-DAFO accounts for its higher permselectivity and
65
Table 2.2. Effect of connector groups on gas separation performance (6FDA-based)
PCO 2 S CO 2 DCO 2
PCO 2 S CO 2 DCO 2
4,4’ – oxydianiline (4,4’ODA) 23 4.89 3.58 60.5 3.70 16.3 0.164 [65]
methylenedianiline (MDA) 19.3 3.96 3.70 44.9 3.36 13.4 0.160 [65]
H
C
H
phenylene thioether (PPTI-1) 23.1 4.96 3.54 34.8 3.84 3.54 0.161 [70]
4,4’-diaminodiphenyl sulfone (pDDS) 16 5.55 0.41 47 3.8 18 0.149 [67]

O
S
O
66
bulky substituents on gas separation performance (6FDA-based)
TableTable
3 Effect
2.3.ofEffect
bulkyofsubstituents on gas separation performance (6FDA-based)
CO 2
PPCO CO 2 CO 2
2 SSCO 2 DDCO 2
P
PCO 2 CO 2 DCO 2
D
Name CO 2 SS CO 2 CO 2 PPCH 4 SS CH 4 DDCH 4 FFV Ref.
Nameand
andchemical
chemicalstructure
structure of
ofdiamine
diamine CH 4 CH 4 CH 4 FFV Ref.
Methylenedianiline
Methylenedianiline(MDA)
(MDA) 19.3
19.3 3.96
3.96 3.70
3.70 44.9
44.9 3.36
3.36 13.4
13.4 0.160 [64]
0.160 [85]
HH
CC
HH
Isopropylidenedianiline
Isopropylidenedianiline(IPDA)
(IPDA) 30 4.24 5.38 42.9
42.9 3.53
3.53 12.1
12.1 0.168 [64]
0.168 [85]
CH
CH3 3
CC
CH
CH3 3
2,2-bis(4-aminophenyl)hexafluoropropane
2,2-bis(4-aminophenyl)hexafluoropropane (6FpDA)
(6FpDA) 63.9 4.7 10.3 39.9
39.9 3.3
3.3 12.2
12.2 0.190 [64]
0.190 [85]
CF
CF3 3
CC
CF
CF3 3
3,6-diaminocarbazole (CDA)
3,6-diaminocarbazole(CDA) 17.1 5.09 2.6 57
57 3.0
3.0 19
19 0.154
0.154 [87]
[66]
HH
NN
N-ethyl-3,6,-diaminocarbazole (ECDA)
N-ethyl-3,6,-diaminocarbazole (ECDA) 33.8 4.79 5.3 33
33 2.8
2.8 12
12 0.161
0.161 [87]
[66]
2H
CC2H 55
NN
Units
UnitsforforP,P,S Sand
andDDare
arebarrer
barrer(1(1barrer
barrer==11xx10
10-10-10cm
cm3 3(STP)-cm/cm
(STP)-cm/cm22sscmHg),
cmHg), cm
cm33 (STP)/cm
(STP)/cm33 atm
atm and 10-8
and 10 -8 cm2 /s respectively
cm2 /s respectively
67
Table 2.4. Effect of polar functional groups on gas separation performance (6FDA-based)
PCO 2 S CO 2 DCO 2
PCO 2 S CO 2 DCO 2
2,7-diaminofluorene (DAF) 11.3 4.64 1.8 54 3.2 1.8 0.155 [71]
H H
C
2,7-diaminofluorenon (DAFO) 7.68 4.48 1.3 60 3.2 1.3 0.154 [71]

O
C
68
lower permeability over 6FDA-DAF [71]. Side appendages with stronger polarity such as
sulfonic groups were substituted on the polyimide main chains to alter the gas transport
properties [64,72-73]. Based on studies related to non-6FDA based sulfonated polyimide
membranes, it was shown that the permeability of and selectivity for CO 2 increase in the
presence of water vapor. This is attributed to the strong interactions between the polymer
chains and CO 2 upon water uptake which facilitates the transport of CO 2 .
In a nutshell, the polymer chain rigidity can be enhanced by integrating (1) meta
linkages, (2) polar side groups, and (3) bridging groups with high energy barrier. Since
the problems of plasticization and physical aging rooted from the flexibility and the non-
equilibrium state of the polymer chains, increasing polymer chain rigidity may reduce the
severity of these undesirable phenomenon. The inter-chain spacing can be increased by
incorporating bulky pendant or bridging groups and designing polyimides with para
linkages. The increase in inter-chain spacing should be coupled with backbone stiffness
in order to achieve both high permeability and selectivity. This strategy is only effective
for certain inter-chain spacings whereby penetrant diffusion is still governed by polymer
segmental motions.
Another feasible approach involves the use of polymers with intrinsic
microporosity (PIMs) which was first disclosed by McKeown’s group [74]. The PIMs
consist of random rod-like structures which generates intrinsic cavities within the
membrane. They exhibit behavior analogous to conventional molecular sieves, but with
69
greater solubility. Due to the intrinsic rotation of the linkages in polyimides structure,
PIMs for this particular class of polymers have not been discovered.
2.2.2 Design of Block Copolymer Systems
One approach to increase CO 2 solubility is to introduce functional groups that
increase CO 2 affinity with the resultant polymer. This is realizable via the synthesis of a
block co-polymer system comprising of desirable segments from different polymers. A
good example is a copolymer consisting of a hard block from a well-packed and rigid
glassy polymer and a soft block based on flexible rubbery polymer as shown in Figure
2.4. [75]. The glassy polymer segments provide the main structural framework and better
thermal resistance while the rubbery segments govern the transportation of gas
molecules.
The CO 2 removal performance of a series of poly(ethylene oxide)
(PEO)/polyimide have been investigated [76-79]. In the work by Okamoto and co-
workers, the PEO/polyimide block copolymers exhibited both high CO 2 permeabilities
and selectivities, possibly due to the improved CO 2 solubility in the PEO segments [76-
77]. Smaihi et al. investigated a series of poly(imide siloxane) copolymers and concluded
that the nature of the coupling agent and the proportion of siloxane significantly affects
the gas permeabilities [79]. Similarly, Hibshman et al. studied a series of poly(imide
siloxane) copolymers and in most cases an enhancement in CO 2 permeability was
achieved but at the expense of CO 2 /CH 4 selectivity [80]. The gas transport properties of a
co-poly(imide pyrrolone), 6FDA-TAB/DAM was studied and the extremely rigid
70
polypyrrolone structure executes molecular sieving function [81]. Most of these co-
poly(imide pyrrolone) membranes exhibited CO 2 /CH 4 separation performances that fall
near to or above the upper bound.
At one instant: (e.g. time = 0)
Hard segments (glassy Soft segments (rubbery

polymer) polymer)
At the next instant: (e.g. time >0)
Configurations of the hard segments Soft segments are flexible

remain the same. Provides the and hence configurations
structural framework change with time
Figure 2.4. Synthetic strategy for copolymer structure for CO 2 separation
2.3 MODIFICATION OF POLYMERIC MEMBRANES FOR GAS
SEPARATION
The synthesis of new materials generally involves risk, high costs and
considerable time. Hence, modification of the existing membrane materials is another

71
viable approach, capable of creating new prospects aimed at overcoming the present
limitations for better separation performance.
2.3.1 Polymer Blending
Polymer blending can be considered as a preferred route of modification in the
light of its simplicity, reproducibility, processability and low development cost.
Moreover, the blending of polymers may synergistically combine the advantages of
different materials. Polymer blends are generally classified as miscible and immiscible.
Miscible polymer blends are the ones desirable for membrane fabrication since
homogeneity is essential to produce membranes with uniform performance while
retaining physical properties.
As mentioned previously, some membranes made of polyimide materials are
seriously susceptible to highly soluble penetrants such as CO 2 . Taking into account the
complimentary features of polyimides and other polymers that possess anti-plasticization
characteristics, it is reasonable to examine the compatibility of these polymers to form
blend membranes with improved properties. Researchers have found that polyimides can
be blended on a molecular level with a number of polymers such as polycarbonate [82],
polysulfone [83], polyethersulfone [84-86], polyaniline [87-88] and polybenzimidazole
[89]. In CO 2 permeation experiments, Kapantaidakis et al. [83] showed that blending
Matrimid with polysulfone (a polymer with significantly higher plasticization pressure)
resulted in anti-plasticization effects. Bos et al. [90] extended this approach to mixed gas
experiments and demonstrated similar improved plasticization behavior, but at the
72
expense of gas permeation and separation performance. In their work, they revealed
another polymer blend system comprising of Matrimid and P84 (a copolyimide) which
can stabilize the membrane against plasticization while simultaneously improving the gas
separation performance [90].
One strategy to make miscible polymer blends is to select polymers which have
strong interactions. Su et al. successfully prepared polyimide/polyaniline blends using the
polyamic acid as a “polymeric” dopant [87]. Gas permeability studies showed that 50/50
polyaniline/polyimide blends provided higher CO 2 permeability compared to the
respective homopolymers. This blend membrane exhibited a corresponding CO 2 /CH 4
separation factor of 85. The separation factors for the polyimide and polyaniline are 59
and 180, respectively [87]. In a recent study, Hosseini et al. carefully selected aromatic
polybenzimidazole (PBI) as the blending material to improve the properties of Matrimid
[89]. It was found that incorporating various amounts of PBI into the Matrimid matrix
can boost the CO 2 /CH 4 separation performance but at the expense of permeability. The
CO 2 /CH 4 selectivity was doubled for the blend comprising 75% of PBI content. PBI is a
high T g glassy polymer that possesses both donor and acceptor hydrogen-bonding sites
[91-93], which are capable of participating in specific interactions [94-95]. The good
processability of Matrimid can compensate for the poor processability of PBI by
controlling a low PBI content in blends. In addition, Matrimid contains electron donating
carbonyl groups which can interact with certain electron accepting groups in PBI and
form strong interactions, as highlighted by Musto et al. [93].
73
Another approach to ensure the miscibility of two polymers involves using a
compatibilzer agent within the membrane matrix. Ekiner and Simmons have proposed
that the addition of the compatibilizer, poly(styrene-co-maleric anhydride) (PSMA)
prevents phase separation within the membranes made of poly(phenylene oxide) and
Nylon 6. The resultant membrane showed good separation performance above the
Robeson’s upper bound for O 2 /N 2 [96]. This approach may be used to fabricate
polyimide blend membranes for CO 2 /CH 4 separation.
Although the promising features of polymer blending were demonstrated, it seems
that the shortage of right pair candidates from the currently available materials is the
limiting factor for further materialization of this technique for gas separation membranes.
In our opinion, the adoption of an approach for the systematic design of suitable pairs is
the most efficient way in revitalizing the true benefits of polymer blending. Based on this,
we foresee good prospects in further utilization of polymer blending of polyimide for
fabrication of high performance membranes.
2.3.2 Hybrid Membranes
Hybrid membrane consists of an organic polymer as the continuous phase and
nano-particles as the dispersed phase. The function of the fillers is to systematically
manipulate the molecular packing of polymer chains, thereby enhancing the separation
properties of polyimide membranes. Typically, the hybrid effects resulting from the
combination of organic and inorganic phases are more prominent when employing fillers
that have smaller dimensions and hence larger surface area. The preparation of nano-
74
composite polyimide membranes can be broadly classified into two categories based on
the state of the fillers before membrane formation. The first type involves the direct
addition of the nano-fillers to a polymer solution. For this direct method, the mixing of
the two phases is accomplished by means of mechanical stirring or ultra-sonication to
reduce particle agglomeration. Thereafter, the organic-inorganic mixture is used for
membrane fabrication. The second approach, also known as the in-situ method entails the
use of nano-particle precursors. For in-situ preparation of nano-composite membranes,
the precursors of the fillers are added to the polymer solution and the nano-particles are
formed during the process of membrane formation. In this approach, the nano-particles
precursors generally have good interactions with the polymer, thereby enabling good
dispersion of the precursor and the resultant fillers [97].
As shown in Figure 2.5., four mechanisms can be proposed to describe how nano-
size fillers may tailor the gas transport mechanism through membranes. Based on the
nature and functional role, the fillers can be classified as: (1) non-porous inert, (2) non-
porous activated, (3) high affinity with polymers, and (4) porous nanoparticles.
Some examples of non-porous inert nanoparticles are fume silica [98], C60 [99]
and polymeric particles [100]. Due to the incompatibility or weak interaction between
these inert particles and the polymer chains, the presence of the fillers disrupts chain
packing and creates interfacial voids between the two phases. The enhanced free volume
in the resultant membrane makes the solubility selectivity as the enhancing factor in the
overall gas separation performance. This is especially effective for the separation of CO 2
75
and CH 4 where the characteristic properties of CO 2 (e.g. condensability and the
quadrupolar nature) can also play a part through enhancing the surface flow [101].
Case 1 Case 2 Case 3 Case 4
Surface diffusion
High
Activated Porous
Inner Filler Affinity
Filler Filler
Filler
Void Rigid
Figure 2.5. Schematic of the various gas transport routes through hybrid
polymeric membranes
Activated carbon particles [102] and ion exchanged zeolites [103] belong to the
group of non-porous activated nanoparticles. Generally, these particles show preferential
sorption for CO 2 by creating a surface flux along the particles. Due to the enhanced CO 2
sorption, the CO 2 /CH 4 permselectivity increases.
Another group of fillers is comprised of non-porous activated nanoparticles such
as metal [104], metal oxides [105] and surface modified zeolites [106]. The high affinity
of these particles with the polymers hinders the mobility of the polymer chains which are
in close contact with the particles. In this case, the presence of the fillers within the
76
polymeric matrix serves a similar purpose as chemical cross-linking since both
approaches reduce the mobility of the polymeric chains. This so called “rigidification
effect” is found to improve the selectivity of membrane.
In the last category, porous nano-size particles such as zoelites [107-108] and
carbon molecular sieves [109] generally integrates the high diffusivity selectivity of
inorganic molecular sieves and good processability of polymeric material. Depending on
the nature of polymer and fillers, the gas separation performance of the resultant hybrid
membranes can be tailored. Detailed discussion can be found in another review related to
mixed matrix membranes [17].
2.3.3 Thermal Annealing
The formation of the glassy polymeric structure from an equilibrium liquid or
rubbery state is a time-dependent relaxation process. It is also well known that the
structure of glassy polymers depends upon their thermal history. The local structure of a
glassy material is expected to change as the conditions of glass formation vary. However,
microvoids or frozen free volume at the glassy state might be retained by glass formation
from the liquid state. In particular, more microvoids or larger specific volume might be
formed if the glass formation is more rapid. Therefore, quenching can be adopted to
enhance microvoid formation [38, 110].
On the other side, the glassy state of amorphous polymer tends to relax towards
an equilibrium state. The relaxation time from the glassy state to the equilibrium super
77
cooled liquid state depends markedly on the temperature of the material. The relaxation
time is very long when the glassy polymers are kept at a temperature far below their T g .
However, the relaxation of the glassy state to the equilibrium state is relatively fast near
the glass transition temperature. Sub-T g annealing, where the sample is annealed near,
but below T g , can provide a state much closer to equilibrium. This translates to a
decrease in the frozen free volume or microvoids of glassy polymers which in turn can
potentially reduce the physical aging effects seem in polyimide membranes for natural
gas separation. Using dense aromatic polyimide 6FDA-m-DDS films, Kawakami et al.
[111] observed that heat-treatment at temperatures well below the T g densified the films.
Both density and glass transition temperature were found to increase with higher thermal
treatment temperatures. In addition, lower gas permeabilities were observed when
compared to untreated film. Similar phenomena have been reported by Krol et al. [112],
Chung et al. [113], Zhou and Koros [114], and Qiao et al. [115]. Polyimides contain
alternating electron donating and electron accepting groups which are able to form the
charge transfer complex. The electron donating molecules correspond to the six-
membered ring (benzene ring) and the electron accepting molecules correspond to the
five-membered ring (imide ring). When the rings approach to the proximity of each other,
π-electron interactions occur, forming a complex which restricts the polymer chain
mobility. The formation of such complexes by thermal curing was proven by
fluorescence and UV-Vis spectroscopy [111-112, 114-115]. As a result of thermal curing,
higher chain packing density, smaller free volumes and slightly higher T g values were
obtained. The suppression of CO 2 -induced plasticization was observed as another
consequence of thermal curing.
78
2.3.4 Grafting and Halogenation of Polymer Backbone
Modification of the pure polyimide membrane by means of chemical grafting
which involves the reaction of suitable reagents with the carbonyl groups via covalent
bonding can be achieved [116]. It is expected that such chemical modification can
substantially alter the gas transport properties of the membranes. For example, Liu et al.
reported the amidation of polyimides by immersing the dense films in a 10% (w/v) N,N-
dimethylaminoethyleneamine (DMEA) dissolved in hexane [117]. This chemical
modification involves the opening of some imide rings to form ortho-diamide, as shown
in Figure 2.6.
NH
R
NH F3C CF3 O
O C C C
NH NH R1
C C O
F3C CF3 O O
O NH
C C C H2N-R-NH2
R1 N R
H2 N N R2
C NH
C
O O F3C CF3
O
6FDA moiety C C C O
N
R: N,N-dimethylaminoethyleneamine [137] C C O
O
HN R NH2
p-xylenediamine [157-161]
ethylenediamine [162]
1,3-cyclohexanebis(methylamine) [163]
PAMAM dendrimers [164-166]
Figure 2.6. Amine modification of polyimides
It was found that amidation significantly reduces the gas diffusion coefficients,
probably due to stronger intersegmental hydrogen bonding between the newly formed
79
amide groups and space filling effects of DMEA. However, the effect of amidation on
CO 2 /CH 4 selectivity depends on the chemical structure of the polyimide; for polyimide
with high side group density (e.g. 6FDA-Durene), the space filling by DMEA reduces the
gas solubility which in turn reduces CO 2 /CH 4 gas selectivity. For polyimide with low
side group density (e.g. 6FDA-durene/mPDA), diffusion dominates the overall gas
transport; the denser packing of intermolecular chains increases the diffusion selectivity,
leading to better CO 2 /CH 4 discrimination. Beside amines, other reagents like hydrogen
cyanide and phosphorus ylides can similarly be grafted to polyimides for better CO 2 /CH 4
separation performance [116].
Alternatively, the benzene rings of aromatic polyimides can be used as functional
sites for side group grafting via electrophilic aromatic substitution reaction. However,
due to the strongly deactivating effects of neighboring carbonyl groups, only the benzene
rings of the diamine unit could be grafted. Bromine atoms were first introduced into
polyimides by Okamoto et al. [128] and Liou et al. [129] using the free-radical
bromination of alkyl groups and the polymerization of halogen-containing monomers,
respectively. Subsequently, Guiver et al. [130] introduced the direct bromination of
Matrimid by electrophilic bromination. The special characteristics of brominated
polyimides are the improved solubility by reduction in chain packing and increased
reactivity.
The fluorination of polyimide films with fluorine, fluorine-helium, fluorine-
nitrogen and fluorine-oxygen gas mixtures has also been reported [131]. However, the
80
degree of fluorination is limited to the immediate contactable surface. A fluorine-treated
film is comprised of fluorinated and untreated layers which are separated by a very thin
layer in which the main chemical transformations proceeds. The major changes occurring
during fluorination of polyimides are: 1) replacement of hydrogen atoms by fluorine, 2)
saturation of double bonds by fluorine, 3) disruption of at least one C-N bond in imide
ring and 4) significant increase in the polymer density. Although the He/CH 4 separation
performance of the fluorinated Matrimid surpasses the trade-off line but the potential
application of this technique for CO 2 /CH 4 separation has remained unexplored.
2.3.5 Cross-linking Modification
The extent of cross-linking and distribution of the resultant network can
profoundly affect the physical properties of polymeric membranes. Generally, it is
believed that cross-linking can be used to 1) increase the membrane stability in the
presence of aggressive feed components, 2) suppress CO 2 -induced plasticization, and 3)
achieve better gas separation properties. Cross-linking modifications of polyimides can
be induced by several methods, such as ultraviolet (UV) and ion beam radiations, thermal
treatment and chemical modification.
Kita at el applied UV radiation to induce cross-linking reactions in
benzophenone-containing polyimides [132]. Depending on the duration of the irradiation,
a considerable improvement in the gas pair selectivity could be achieved but with greatly
reduced gas permeability, presumably due to densification of membrane structure and
reduced mobility of polymer chains. Won et al. and Hu et al. investigated the effects of
81
surface modification of polyimide membranes by ion beam [133-134]. They concluded
that ion beam irradiation could provide a useful mean for improving selectivity for gas
separation membranes. Despite the potential use of ion irradiation in enhancing gas
separation pair permselectivity, the high cost and difficulty in implementing uniform
irradiation on large sheets of flat membranes and hollow fibers limit the industrial
application of this technique.
Cross-linking through heat treatment has been studied extensively on polyimide
membranes. It was shown that thermal annealing at elevated temperatures for short
periods of time can significantly induced cross-linking in 6FDA polyimide [113] and
Matrimid films [135]. Polyimides containing acetylene groups have also been
investigated and cross-linking occurs via a Diels-Alder type reaction under heat treatment
[136-137]. The cross-linking modification improved gas selectivity with an acceptable
decrease in gas permeability and significantly enhanced CO 2 plasticization resistance.
Another approach for improving the resistance of polyimide membranes involves
the formation of semi-interpenetrating polymer networks, obtained by heating a mixture
of polyimides with monomers or oligomers containing reactive groups with the ability to
crosslink (e.g., acetylene end groups). Rezac et al. [138] blended 6FDA-IPDA with a
diacetylene containing oligomer (6FDA-DIA) and cross-linking was achieved by heating
the membranes to 340oC. The crosslinked polyimides rendered better
permeability/permselectivity results. Semi-interpenetrating networks derived from blends
82
of Matrimid and the oligomer containing acetylene groups, Thermid FA-700 also showed
good plasticization resistance [139].
Koros, Paul and their co-workers have synthesized carboxylic containing
polyimide membranes which can be cross-linked by either a transesterification reaction
or reaction with a metal ion [140-144]. The effect of cross-linking the polyimide depends
on the chemical structure of the diol cross-linking agents and the specific annealing
temperatures. Unlike other cross-linking modifications which typically decrease the
permeability of the resultant polymeric membranes, cross-linking of carboxylic
containing polyimides with ethylene glycol can lead to an increase in the permeability
without sacrificing selectivity. It should be noted that transesterification occurs only at
elevated temperatures (above 200oC). The increase in the free volume may be due to the
coupling of thermal annealing and the removal of pendant diol groups during the
transesterification reaction. The aging phenomenon of these cross-linked membranes
(thermally treated at 140 oC) has been investigated by Kim et al. [144] and it was found
that the polyimide membranes suffered more from physical aging after cross-linking.
This is perhaps attributed to the incomplete transesterification reaction at a low
temperature of 140oC. The cross-linking reaction may proceeds continuously during the
gas permeation testing which accounts for the decline in gas permeability with time. This
problem can be rectified by performing the cross-linking reaction at elevated
temperatures. Nevertheless, the application of high temperature treatments to asymmetric
membranes alters the membrane morphology and causes densification of the membrane
structure. It should be noted that crosslinking of the bulk polyimide matrix reduces the
83
polymer processability during membrane fabrication and increases the brittleness of the
resultant membranes. Therefore, the preferred cross-linking method should have the
following characteristics: (1) can be performed at room temperature and (2)
functionalizes only the thin selective layer of asymmetric membrane which reduces
substructure resistance and brittleness of the support layer.
Another chemical modification method has been proposed to overcome the
difficulties of post-treatment processes. Hayes devised a new way of cross-linking by
immersing polyimide in a diamino compound solution [118,145]. This approach by
Hayes was first employed for increasing O 2 /N 2 selectivity which was further explored by
Chung’s group. Chung and his co-workers have contributed a number of works related to
the use of diamines and multi-amines to cross-link polyimides [119-127,146-147]. The
results obtained from these works are summarized in Tables 2.5. and 2.6. A typical
mechanism for such cross-linking has been shown in Figure 2.6. Liu et al., Cao et al. and
Tin et al. used p-xylenediamine as a cross-linking agent to modify different polyimide
hollow fiber membranes at ambient temperature [119-122]. It is proven that the
chemically modified membrane does not plasticize easily since the cross-linked structure
prevents the material from swelling in the presence of plasticizing agents. Generally,
increasing the immersion time increases the degree of crosslinking which significantly
reduces polymer swelling and chain mobility. Hence, enhancement in the CO 2 /CH 4
permselectivity may be achieved. Compared to the ethylene glycol approach, the diamine
and multi-amine approaches are more advantageous especially for the modification of
hollow fibers because of easy operation and localized chemical modification at the outer
84
Table 2.5. CO2/CH4 separation performance of crosslinked dense films
Polyimide Temperature Pressure Crosslinking agent and immersion time PCO2 αCO2/CH4 Reference
(oC) (atm) (Barrer)
Matrimid® 35 10 No modification 6.5 34 [123]
5218
10 (w/v)% p-xylenediamine in methanol, 24 h 7.4 36
6FDA-durene 35 10 No modification 600 15 [124]*
10 (w/v)% ethylenediamine in methanol, 2 min 100 28
10 (w/v)% 1,3-cyclohexanebis(methylamine) 55 19 [125]
in methanol, 30 min
10 (w/v)% G1 diaminobutane dendrimer in 430 22 [127]*
methanol, 5 min
5 (w/v)% G0 polyamidoamine dendrimer in 20 47 [126,146]
methanol, 10000 min
5 (w/v)% G1 polyamidoamine dendrimer in 300 30 [146]*
methanol, 10000 min
5 (w/v)% G2 polyamidoamine dendrimer in 370 29
methanol, 10000 min
* Values are approximated from plots
P: permeability
Barrer = 1×10−10 cm3 (STP)-cm/cm2 s cmHg = 7.5005 x 10-18 m2s-1Pa-1
85
Table 2.6. CO2/CH4 separation performance of crosslinked hollow fibers
Polyimide Temperature(o Pressure Crosslinking agent and (P/l)CO2 αCO2/CH4 Reference

C) (psi) immersion time (GPU)
6FDA-durene/mPDA 23 CO2: 100 psi No modification 70.4 44 [121]

(50:50) (selective layer) CH4: 200
5% (w/v) p-xylenediamine in 28.3 101
– PES (inner layer) psi
methanol, 5 min
6FDA-2,6-DAT 25 Mixed gas No modification 55 60 [120]
– single layer CO2 (40%)
1% (w/v) p-xylenediamine 19 63
and CH4
in methanol, 3 min
(60%), total
pressure: 1% (w/v) m-xylenediamine 18 59
200 psi in methanol, 3 min
6FDA-ODA/NDA 25 CO2: 50 psi 5% (w/w) p-xylenediamine in 30 58 [122]
(50:50) – single layer CH4: 200 methanol, 24 h
psi
(P/l): Permeance
1 GPU = 1x10−6 cm3 (STP)/cm2 s cmHg
86
selective skin without damaging the entire membrane substructure.
Chemical modifications of 6FDA-durene dense membranes were performed using
a linear aliphatic diamine, ethylenediamine (EDA) [124] and a bulky diamine, 1,3-
cyclohexanebis(methylamine) by Shao et al [125]. Low temperature thermal annealing
(100~150oC) was utilized to facilitate the amidation reaction. The coupling effects of
diamine-induced cross-linking and thermal annealing accelerates the formation of charge
transfer complexes (CTCs) which densifies the polyimide membrane structure. As a
result, the gas transport properties of the modified polyimides generally show reduced
permeability and enhanced selectivity upon cross-linking and thermal annealing. CO 2
plasticization tests on the resultant membranes indicate that the coupling effects of cross-
linking and thermal annealing can also improve the plasticization resistance of 6FDA-
durene membranes from around 300 psia to more than 720 psia, which may be attributed
to the effective formation of CTCs.
Chung, Xiao and their co-workers modified 6FDA-polyimide membranes using
G0, G1 and G2 PAMAM dendrimers which have multi-functional groups [126-127,146-
147]. Compared with the simulated results, the morphology and conformation of the
grafted PAMAM dendrimers on the polymer surfaces are disk-shaped molecular clusters
which were further proven by AFM. In fact, immersion time and different dendrimer
generation are two important factors in determining the characteristics of modified
polyimide films. A longer immersion time yields higher dendrimer loading and
equilibrium may be reached after modifying for at least 24 hours. Due to their big
molecular size, the cross-linking modification was believed to occur mainly on the
87
membrane surface. The modified polyimide films also exhibited better gas separation
performance, especially for CO 2 /CH 4 because of the affinity between PAMAM
dendrimer and CO 2 . In another study, the effects of temperature on the multi-amine
modification have been investigated [147]. Thermal treatment at temperatures below 150
o
C facilitated the amidization reaction between the polyimide and dendrimers and
enhanced the degree of cross-linking by the dendrimers. On the other hand, high
temperature treatment (>250oC) destroyed the cross-linked structures of the modified
polyimide via the decomposition of the dendrimer molecules and the degradation of the
polyimide backbone.
Although the amino-modification of polyimide membranes enhances CO 2 /CH 4
permselectivity, the long term operational stability of the membranes remains unclear.
One drawback of this approach is the reversible reaction between the amino-compounds
and the imide groups at high temperatures which has been verified by Powell et al. [148-
149]. Nevertheless, the modified membranes can be employed for CO 2 /CH 4 separation at
relatively mild operating temperatures. In addition, since the amidation reaction is carried
out at room temperature, the reaction may be incomplete which result in time-dependent
gas separation performance of the resultant membranes. Moderate temperature (~150oC)
treatment has been approved to facilitate the amidation reaction [125,147]. More studies
on the long-term stability of the modified membranes are required.
2.4 CURRENT AND FUTURE DEVELOPMENTS
88
An ideally structured polyimide suitable for fabricating high performance
CO 2 /CH 4 separation membranes should possess the characteristics of backbone stiffness
coupled with large inter-chain spacing. The basis of this claim is that diffusivity
selectivity plays a dominant role in the separation of CO 2 /CH 4 . It is believed that these
characteristics will result in polyimide membranes with remarkable CO 2 permeability
and CO 2 /CH 4 permselectivity. Current studies on the molecular design of polyimides
tend to accomplish this via employing 6FDA because the CF3 groups considerably
increase the stiffness of the chain on the basis of steric bulk hindrances and effectively
reduce the chain packing. However, there is no significant improvement in gas separation
performance beyond the upper bound. Due to the intrinsic rotation of the linkages in
polyimide structure, it seems difficult to increase the inter-chain spacing without losing
backbone stiffness. In view of the current state of novel polyimide development for
CO 2 /CH 4 separation, researchers should perhaps divert their attention towards enhancing
the solubility and solubility selectivity in the design of new polyimides. Possible
strategies to achieve this include the incorporation of functional groups into capable of
increasing the affinity of CO 2 to the polymer and creating more sorption sites for CO 2 .
In consideration of the higher stiffness of inorganic materials, many researchers
attempt to transform polyimide to carbon state by high temperature pyrolysis [150-153].
In this way, the gas transport switches from solution-diffusion to primarily molecular
sieving. As a result, the gas separation performance surpasses the upper bound. Other
than the high cost of carbon membrane, another critical problem is its brittleness which
89
makes its processing difficult. Detailed information about carbon membrane derived from
polyimides could be found in another review [154].
Recently, Islam et al. proposed a low-temperature pyrolysis method for
fabricating flexible organic-inorganic intermediate membranes by the cleavage of SO 3 H
groups in the sulfonated polyimides [155]. The resultant membranes possess attractive
gas separation performance with high degree of flexibility. As an extension of this idea,
Park et al. suggested the systematic tailoring of an unusual microstructure via thermally-
driven “molecular rearrangement” process [67]. In this process, the single bond linkages
of the polyimide are changed to stiff and rigid chain elements (e.g. benzoxazole-
phenylene ring or benzithiazole-phenylene ring). Additionally, the indiscriminant
torsional rotation increases the efficiency of free volume formation. Consequently, the
gas separation performance of such membranes can surpass the upper bound.
Nonetheless, it is important to keep in mind that this approach similarly requires thermal
treatment at elevated temperatures which may limit its application to asymmetric
membranes.
In addition to good gas separation performance, the durability and the lifetime of
the polyimide membranes are also important. Aging and plasticization phenomena create
undesirable time dependency of the gas separation performance for polyimide
membranes. In order to improve the stability of membrane, thermal annealing, polymer
blending and cross-linking can be employed. However, for successful commercial
application of membrane-based natural gas treatment using polyimides, hollow fiber
90
processing and the overall costs must be adequately tuned. Therefore, the discussed
methods are still a distance away from the requirements. The focus of polyimide
membrane research in the near future may remain on new polyimide molecular
architectures and seeking better cross-linking agents which can work under low
temperature and only at the surface layer to obtain desirable membranes for CO 2 /CH 4
separation. Significant research efforts must be tilted to asymmetric flat and hollow fiber
configurations rather than dense flat membranes in order to have real and immediate
impact on scale up and commercialization.
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CHAPTER THREE
ENHANCED GAS SEPARATION PERFORMANCE OF NANOCOMPOSITE
MEMBRANES USING MGO NANOPARTICLES
3.1 INTRODUCTION
After the emergence of commercial membranes for separation, this technology
has yet been firmly struggling to establish its position as the preponderant choice for
various applications. During this time span, membrane technology has been the subject of
numerous investigations in various aspects which has led to the better performance and
broader range of applications. After successful achievements in this field, nowadays,
membranes have found their proper candidates in various types of liquid and gas based
separations. Low operation cost, relatively small footprint, low energy requirement and
consortion with environmental regulations are of the major benefits of membranes over
their conventional counterpart technologies. Membranes have been successfully
developed for separation of gas molecules and they are widely used in chemical and
petrochemical plants. Separation of hydrogen from its mixtures with nitrogen or
hydrocarbons, nitrogen purification and the foremost CO 2 removal from natural gas are
recognized as major established and high value industrial applications of membranes.
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Different types of materials have been used in the membrane fabrication, where
polymers have attracted more attentions. This is mainly due to the low production cost
and ease of processing, especially for making them in the form of hollow fibers which
offer membranes with higher surface area per unit volume. However, conventional
polymeric membranes generally suffer from the trade-off limitation between productivity
and selectivity which yet remains as one of the most important challenges for further
developments in this field [1]. Different methodologies have been adopted by researchers
in the architecture andmodification of polymers as well as fabrication technology in order
to overcome the shortcomings of polymeric membranes.
Nanocomposite membranes (also known as mixed matrix membranes) and
facilitated transport membranes (FTM) are two distinguished and promising generations
of gas separation membranes which have attracted considerable amount of attention for
their potential use in gas separation and purification.
The microstructure of a nanocomposite membrane is commonly composed of an
inorganic material, in the form of micro- or nanoscale particles, as the discrete phase, and
a polymeric material which forms the continuous or matrix phase. The successful features
of nanocomposite membranes are mainly beholden to the synergistic combination of easy
processability of polymers and superior gas separation factor of inorganic materials. In
addition they may offer enhanced physical, thermal and mechanical properties for
aggressive and adverse environments [2,3]. Some studies also indicated that the particles
110
added into the polymer matrix might have a hope of stabilizing the polymer membrane
against change in permselectivity with temperature [4].
Several inorganic materials have been proposed as good candidates for the
fabrication of nanocomposite membranes. These materials are generally categorized into
two major classes of porous and nonporous fillers. Each type of these materials offer
distinguished transport mechanisms to the membrane.
Zeolites are probably the frontier family of molecular sieves and have been
widely used in both rubbery and glassy polymers for gas separation membranes [5-11].
Zeolite filled membranes from rubbery polymers showed significantly improved
performance for separation of oxygen/nitrogen and carbon dioxide/methane compared to
their pristine polymeric membranes [6,7]. However the use of zeolites with the glassy
polymers has confronted some obstacles specially in controlling the polymer-particle
interface [10-14]. Studies on zeolite-based nanocomposite membranes using glassy
polymers have revealed the pivotal roles of polymer-zeolite affinity at interface on the
resultant gas separation performance; therefore, applying some modification techniques
has resulted in progress in this area [9-11,15,16].
Carbon molecular sieves (CMS) are considered another candidate which exhibit
excellent intrinsic performance for gas separation processes. This micro to nano-size
materials are generally obtained through the pyrolysis of polymeric precursors. CMS
materials can be used as membranes directly or after milling be introduced into a
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polymeric matrix to form nanocomposite membranes. It is well documented the
polymeric precursor plays a crucial role in the performance of CMS and extensive
researches have been carried out on the preparation of CMS from both rubbery and glassy
polymers using different techniques [17-23].
On the other hand, metal oxides nanoparticles have also important materials due
to their potential applications for membrane-based separation purposes. Moaddeb and
Koros [24] prepared composite membranes by introduction of silicon dioxide particles
into the matrix of six high performance polymers. They found that presence of silica
improves the gas separation performance of the selective layer particularly for oxygen
and nitrogen. This was mainly attributed to the enhanced rigidity of polymer matrix due
to the adsorption of polymer chains to the surface of silica.
Hu et al. [4] developed nanocomposite membranes based on fluorinated
poly(amide-imide) polymer matrix and TiO 2 component via sol-gel technique. These
composite membranes similarly showed higher permselectivities for selected gas pairs
when compared to the neat polymeric counterpart membrane. They attributed the results
to the denser and more rigid structure of the composite membranes which detected by the
increase in apparent activation energy of permeation.
Very recently, Lin et al. [25] introduced the use of MgO nanoparticles in the form
of nanocomposite membranes for CO 2 /H 2 separation. In the optimum condition, they
achieved significantly improved CO 2 permeability while maintaining selectivity by
112
loading around 32wt% of magnesium oxide nanoparticles into the crosslinked
poly(ethylene glycol) diacrylate matrix. The enhanced CO 2 permeability was ascribed to
the effect of nanoparticles on gas diffusivity.
Similar to the nanocomposite membranes, FTMs have also shown promising
results for gas separation. The structure of FTM is designed in a way that some particular
carriers inside the membrane may have the special affinity toward the target gas
molecules and this interaction controls the rate of transport. The majority of the carrier
candidates introduced by the researchers are in the class of metal ions. Generally, the
application of ions for membrane-based gas separation can be categorized into four major
types of immobilized liquid membranes, ion exchange membranes, polymer/metal ion
blends and modified polymer membranes [26-29]. Limitations associated with
immobilized membranes concerning operating conditions [27,28] led to the emergence of
ion exchange membranes. Way et al. prepared ion exchange membranes containing
organic amine counter-ions which showed enhanced performance for CO 2 removal from
its mixture with methane [30].
The application of silver ions has been extensively studied as a promising carrier
for the fabrication of FTMs. It is well documented that the presence of some special
metal ions like Ag+ facilitates the transport of olefins. This is ascribed to the ability of
silver ions to form reversible π-complexation with double-bond gas molecules, leading to
a subsequent solubility enhancement. Therefore, this mechanism has been successfully
exploited as facilitated transport membranes for olefin/paraffin separation [31,32]. As a
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result, selection of suitable carrier with high affinity toward the desired molecules, in
conjunction with the adoption of appropriate strategy for design and fabrication of
membranes are of the principal criteria to wield the advantages of facilitated transport for
gas separation.
The presence of affinity and interaction between MgO surface and some gas
species like carbon dioxide [33] provides a great motivation to investigate the potential
application of this material as carriers in FTM structure for separation of gas molecules.
In addition, research results have shown that MgO surface has a good adsorption affinity
toward transition metals which is highly advantageous for alteration of surface properties.
Klabunde et al. [34] demonstrated magnesium oxide nanocrystals containing a monolayer
of a transition metal oxide on the surface have greatly enhanced efficiency for the
adsorption of chlorocarbons, hydrogen sulfide, and sulfur dioxide. Therefore, it seems to
be a novel idea that one combines the superior performance of nanocomposite and
facilitated transport membranes together in a single membrane. The objective of this
research study is to develop high performance nanocomposite membranes for hydrogen
separation and CO 2 removal from natural gas by combining the features of inorganic and
organic materials. Nanocomposite membranes were fabricated by a solution-casting
method with different loadings of MgO nanoparticles. Matrimid, a commercially
available glassy polymer with high T g was selected as the continuous phase for all
nanocomposite membranes. Matrimid possesses high gas permeability and selectivity as
well as high thermal stability and solvent resistance properties [35-37]. Firstly, the
characteristics of both MgO and its derived membranes were evaluated by various
114
techniques. The effects of MgO loading on structure-property relationship and gas
separation performance of these membranes were examined. Secondly, these membranes
were post-treated with silver nitrate solution for stipulated periods of time. The effects of
silver treatment and immersion time on gas separation performance of Matrimid-MgO-
Ag+ nanocomposite membranes were investigated. To our best knowledge, this is the first
study that combines the synergistic features of nanocomposite structure and facilitated
transport mechanism into one membrane by using unique characteristics of MgO for gas
separation.
3.2 EXPERIMENTAL
3.2.1 Materials
The polyimide (Matrimid5218) was purchased from Vantico Inc., (Luxemburg).
The solvents including N-methyl-2-pyrolidone (NMP) and methanol were supplied by
Merck and were used without further purification. The magnesium oxide nanoparticles
(NanoActive MgO Plus) were purchased from Nanoscale Materials Inc. (Manhattan,
Kansas). The physical properties of magnesium oxide nanoparticles are shown in Table
3.1. Silver nitrate solid with a reagent grade was supplied by Merck. Both polymer
powders and MgO nanoparticles were dried overnight at 120oC under vacuum prior to
use.
115
Table 3.1. Properties of magnesium oxide (MgO Plus) nanoparticlesa
Property Value
Specific surface area (BET) > 600 m2/g
Crystallite size < 4nm
Average pore diameter 30 Å
Total pore volume > 0.4 cc/g
Mg content (based on metal) > 99.2 %
True density 2.4 g/cc
aData obtained from the manufacturer’s MSDS.
3.2.2 Membrane fabrication
Since MgO is very susceptible to water adsorption and agglomeration, the
nanoparticles were firstly dried under vacuum for overnight and then stipulated amounts
of MgO nanoparticles were sifted on a 20μm-size test sieve (Retsch®, Germany) to
remove any coarse agglomerates. The fine particles were then dispersed in NMP under
continuous stirring for about an hour followed by sonication for 5 min to break any
aggregation and improve the dispersion quality. The polymer powders were then
gradually added up to 20wt% concentration and the stirring was continued for at least one
day to achieve a homogenous solution. The high polymer concentration was selected in
order to prevent the sedimentation of MgO nanopaticles during the casting. Matrimid-
MgO nanocomposite membranes were fabricated via solution-casting at high
temperatures followed by natural cooling. The technique adopted here was similar to the
one previously developed in our group [15]. The maximum loading of MgO was set to
40wt% due to the handling problems and brittleness of MMMs at higher loadings.
116
3.2.3 Post-treatment of membranes
Nanocomposite membranes containing 20wt% MgO underwent various heat
treatment steps. Small pieces of samples were heat treated in a precise furnace under
vacuum condition at different temperature profiles of below and above the glass
transition temperature of the polymer matrix (Matrimid T g =318˚C). The effect of cooling
profile was also investigated by applying two distinguished procedures. For the course of
natural cooling, the samples were allowed to reach the room temperature by turning off
the heating source. During this step, the samples remained under vacuum. In contrast,
other counterpart samples were quenched inside the liquid nitrogen immediately after
removing from the furnace. They were further dried under vacuum before permeation
tests.
Silver treatment was carried out through a dip coating technique. Firstly, silver
nitrate grains were dissolved in methanol. A saturated solution was obtained after stirring
for almost one hour. A piece of membrane was cut and immersed in this solution for a
certain period of time. Afterwards, silver treated membranes were washed in fresh
methanol to remove the residual and unused silver ions. Membranes were dried at room
temperature followed by vacuum drying at 150oC overnight to eliminate any trace of
methanol. Finally, membranes were cooled naturally and were ready for characterization
and gas permeation tests.
3.2.4 Membrane characterizations
117
The morphology of membranes was examined by scanning electron microscope
(SEM). The electron micrographs were obtained on a JEOL JSM-5600LV and JSM-
6700F. Both Energy dispersive X-ray (EDX) and X-ray photoelectron spectroscopy
(XPS) techniques were employed for elemental analysis of membranes. EDX analysis
was carried out using Oxford Instruments Inca EDX system equipped with SEM
machine. XPS data were acquired on a Kratos AXIS-HSi spectrometer with built-in
charge neutralization system. A dual anode Al/Mg X-ray source was operated at 300W
(15 kV, 20 mA).
The structural properties and inter-chain spacing of membranes were analyzed
qualitatively on an X’Pert PRO-MRD wide-angle X-ray diffractometer (XRD) from
PANalytical. The measurements were carried out by using Cu Kα radiation with a
wavelength of λ = 1.54Å at room temperature. The scan range was from 5 to 85

˚ with a
step increment of 0.04̊/s. Average d-spacing was determined based on the Bragg’s law,
viz.
nλ = 2d sin θ (3.1)
where n is an integral number (1, 2, 3, ...), λ denotes the X-ray wavelength, d stands for
the intersegmental spacing between two polymer chains and θ indicates the diffraction
angle.
3.2.5 Gas permeability measurements
The gas permeation properties of membranes were determined by a variable-
pressure constant-volume method. Detailed experimental design and procedures can be
118
found elsewhere [38]. The thickness of membranes used for permeability measurements
was about 50μm. The rate of pressure increase (dp/dt) at steady state was used for the
calculation of gas permeability with the following Eq. (3.2):
273.15 × 1010 Vl  dp 
P=   (3.2)
760 AT (( P0 × 76) / 14.7)  dt 
where P is the gas permeability of a membrane in Barrer (1Barrer = 1×10-10cm3 (STP)-
cm/cm2.sec.cmHg), V is the volume of the down-stream chamber (cm3), A refers to
effective area of the membrane (cm2), l is the membrane thickness (cm), T is the
operating temperature (K) and finally pressure of the feed gas in up-stream is given by P 0
in psia.
The pure gas permeability was obtained in a sequence of He, H 2 , O 2 , N 2 , CH 4
and CO 2 at 35oC for each nanocomposite membrane. The H 2 permeability test was
conducted at 3.5atm, while the testing pressure for other gases was 10atm. The ideal
selectivity of a membrane for gas A to gas B was evaluated as follows:
PA
α A/ B = (3.3)
PB
3.2.6 Measurement of gas sorption
CO 2 gas sorption tests were conducted for nanocomposite membrane films using
a Cahn D200 microbalance sorption cell at 35 oC over a pressure range of 0-15 atm.
Approximately 100 mg membrane films were placed on the sample pan. The system was
evacuated for 24 h prior to testing. The gas at a specific pressure was fed into the system
and the sample started to sorb the gas until the equilibrium was achieved. From the
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weight gain, the amount of gas dissolved in the membrane was calculated after counting
the buoyancy correction.
3.3 RESULTS AND DISCUSSION
3.3.1 Effect of MgO loading on the gas separation performance of nanocomposite
membranes
Matrimid-MgO nanocomposite membranes with MgO loadings from 20wt% to
40wt% were fabricated according the procedure mentioned in the previous section. For
comparison, one piece of neat Matrimid membrane was fabricated in the form of dense
flat following the same procedure. Figure 3.1. shows a uniform distribution quality of
MgO nanoparticles inside the polymer matrix analyzed by EDX. This figure also
confirms that the dope viscosity has been high enough to prevent the particles from
sedimentation during the membrane formation.
Figure 3.2. exhibits the gas permeability of neat Matrimid and nanocomposite
membranes with different MgO loadings. It can be seen that the permeability of
nanocomposite membranes is higher than that of neat Matrimid membrane. This figure
also shows a monotonous increase in permeability with increasing the MgO content for
all the gases. The average increment in gas permeability is about 75% which is obtained
for the membrane with 40wt% MgO loading. Clearly, the enhancement in gas
permeability is mainly due to the incorporation of highly porous MgO nanoparticles
which are substituted some portions of the dense structure of polymer chains in the
membrane structure.
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Figure 3.1. Dispersion quality of MgO nanoparticles at the surface of the nanocomposite
membrane with 20wt% MgO.
In principle, the increase in permeability of nanocomposite membranes may be
attributed to the presence of microvoids at the polymer-particles interface and/or the
inherent transport properties of porous particles if encompassing pores larger than the
kinetic diameter of gases. The cross-section morphology of nanocomposite membranes
with different MgO loadings is shown in Figure 3.3. The morphological analysis of the
membranes reveals that particles are intimately intercalated inside the polymer matrix
and no macrovoids or defect could be observed at the polymer-particle interface. We
believe, adoption of appropriate casting procedure, controlling of temperature and phase
inversion process, and final cooling profile play important roles in achieving successful
interfacial adhesion between polymer chains and particles.
121
50 4
45 Pure Matrimid Pure Matrimid

3.5
20% MgO Loading 20% MgO Loading
40
30% MgO Loading 3 30% MgO Loading
35 40% MgO Loading 40% MgO Loading
30
2.5
25 2
20
1.5
15
Permeability (Barrer)
Permeability (Barrer)
1
10
0.5
5
0 0
Helium Hydrogen Carbon dioxide Oxygen Nitrogen Methane
Test gas Test gas
Figure 3.2. The comparison of gas permeability for pure Matrimid and nanocomposite membranes with different
loadings of MgO nanoparticles. (left: permeability of helium, hydrogen and carbon dioxide; right: permeability of
oxygen, nitrogen and methane)
122
A B C
Figure 3.3. The cross-section morphology of nanocomposite membranes with different loadings of MgO
nanoparticles. (MgO loadings: A: 20wt% B: 30wt% C: 40wt%). Inset: high magnification image of MgO
nanoparticles inside the polymeric matrix.
123
Therefore, it can be concluded that the permeability increment observed for
nanocomposite membranes are resulted from the contribution of highly porous structure
of magnesium oxide nanoparticles in which all the gas molecules, regardless of size, can
pass through the particles without any resistance against their transport. The separation
performance of membranes was calculated for selected gas pairs. The ideal selectivity
results of the as-fabricated MgO containing nanocomposite membranes are listed in
Table 3.2. These data denote a general ebb in selectivity performance of nanocomposite
membranes compared to the neat Matrimid membrane. This corroborates our reasoning
for the gas permeability results and reveals that the pore size (30 Å) of MgO
nanoparticles is much larger than the kinetic diameter of gas molecules. As a result, the
porous structure of MgO nanoparticles cannot selectively distinguish the gas molecules
based on their size difference, thus the overall diffusivity selectivity of membranes is
diminished.
Table 3.2. The ideal selectivity of pure Matrimid and Matrimid-MgO nanocomposite
membranes with different nanoparticle loadings.
Membrane name Ideal Selectivity

H2/N2 He/N2 CO2/CH4 O2/N2 H2/CO2
Matrimid®5218 97.0 93.1 33.3 7.14 3.88
Matrimid+MgO(20%) 89.5 86.0 29.8 6.31 3.89
Matrimid+MgO(30%) 89.3 85.5 26.9 6. 28 3.64
Matrimid+MgO(40%) 90.1 86.1 26.4 6.50 4.60
124
3.3.2 Effect of heat treatment on the gas separation performance of nanocomposite
membranes
Membranes containing 20wt% MgO were used to investigate the effect of heat
treatment on the transport and separation performance of nanocomposite membranes. The
results of the gas permeability and selectivity of heat treated membranes are listed in
Table 3.3. Two distinct behaviors are detected with respect to the treatment temperature.
A considerable reduction in gas permeability values are observed for the membranes heat
treated at 240˚C. However, the permeability was significantly increased for the samples
heat treated at 350˚C. In comparison with the results obtained from untreated membranes,
it seems that heat treatment at the temperature below the polymer T g has resulted in the
densification of the polymeric matrix; thus diminishing free volumes and bringing about
more resistance for the gas transport across the membrane. On the other hand, heat
treatment above the T g of polymer provides more freedom in the mobility of polymer
chains which results in the increase in fraction of free volume in the membrane structure.
Furthermore, it was observed that the sample with immediate quenching exhibited even
further increased permeability. From the structural point of view, this can be attributed to
the fact that natural cooling provides polymer chains sufficient time for rearrangements
and position themselves more ordered structure. Therefore, this process annihilates some
portion of the generated excess free volumes. However, in the sample with quench
profile, generated free volumes instantly become frozen at the incipient point of cooling.
The results are well in agreement with the study of Tsujita [39] on the behavior of glassy
polymers toward thermal conditioning. It is interesting to note that the selectivity
performance of the membranes with different treatment profiles remained unchanged in
125
Table 3.3. The effect of heat treatment and cooling profile on the permeability and selectivity of Matrimid-MgO nanocomposite
b
Membrane: Permeability (Barrer) Ideal Selectivity
Matrimid-MgO(20%)
Heat treatment Cooling
condition profile He H2 O2 N2 CH4 CO2 H2/N2 He/N2 CO2/ CH4 O2/N2
Untreated - 31.0 32.2 2.27 0.360 0.278 8.27 89.5 86.0 29.8 6.31
Heat treated at
Natural 25.3 27.0 2.06 0.319 0.245 7.36 84.6 79.3 30.0 6.46
240˚C for 12 hrs
Heat treated at
Natural 37.6 41.2 3.22 0.503 0.389 10.78 81.9 74.8 27.7 6.40
350˚C for 1 hr
Heat treated at
Quench 41.1 44.7 3.31 0.520 0.406 11.64 86.0 79.0 28.7 6.37
350˚C for 0.5 hr
1 Barrer = 1*10-10 cm3(STP) cm/cm2 s cm Hg
Testing Temperature 35oC
126
the same range. This may imply that the intimate interface of polymer-particle has been
in its perfect initial condition.
3.3.3 Effect of MgO nanoparticles on silver adsorption into the nanocomposite
membranes
Membranes containing 20wt% MgO loading were immersed inside the silver
nitrate solution for stipulated period of time. One piece of neat Matrimid membrane was
also treated with silver ions for comparison. Different techniques were used to analyze
the characteristics and structural changes of membranes after silver treatment. Visual
observation indicated that all nanocomposite membranes were discolored from yellowish
to brownish after silver treatment. The discoloration was only observed for the
membranes containing MgO nanoparticles while the color of neat Matrimid membrane
remained intact. Taking into account the natural color of silver element, the observed
discoloration suggests that some interactions have been taken place between membrane
and silver ions. The uniformity of the brownish color throughout the membrane structure
may be a sign of successful penetration of silver ions into the nanocomposite membranes.
In addition, it was found that the intensity of brownish color was higher for the
membranes with longer immersion time which inarguably denotes the presence of higher
concentration of silver ions at the prolonged immersion time scales.
EDX analysis was conducted to further elucidate the state and adsorption of silver
ions into the nanocomposite membrane. Figure 3.4. shows a comparison in profiles of
elementary analysis for Mg and Ag elements which was performed at the cross-section of
127
membranes with a 20wt% MgO loading after silver treatment for different periods of
time. The result of silver tracing inside the silver treated neat Matrimid membrane is
depicted in this figure. Application of elemental line mapping at the cross-section of
membranes suggests that silver cations have successfully penetrated into the whole
structure of nanocomposite membranes. One can see that the intensity of the peaks was
increased for the samples with longer retention time; indicating an increase in population
of silver cations as a function of time. However, it is clear in Figure 3.4. that much less
silver ions have penetrated into the neat Matrimid membrane. This may suggest that there
is almost no sensible interaction between the elements in polymer chains and silver ions.
In other words, the polymer itself may not exert any attractive force to draw the silver
ions into the membrane. These results lead us to conclude that the main driving force
causing the migration of silver ions from the solution into the nanocomposite membranes
have been induced by MgO nanoparticles. This can be confirmed by careful scrutiny of
EDX profiles where the peaks of Mg and Ag elements have been appeared in
corresponding locations and follow the same trend. As a result, a close consistency in the
locus and concentration of these two elements can be drawn. This indicates that the major
adsorption of silver elements takes place onto the sites provided by MgO nanoparticles.
The surface properties of neat Matrimid and nanocomposite membranes were
studied using XPS. Data in Table 3.4. present the binding energy values of C, N, and O
elements for the neat Matrimid membrane before and after silver treatment. As it was
expected based on the previous results, the amount of silver ions attached to the
membrane was not high enough to be detected by XPS. In addition, no significant
128
Figure. 3.4. The elementary profiles of EDX analysis for the pure Matrimid and nanocomposite membranes (20wt% MgO
loading) after silver treatment for different periods of time (Upper row: Ag element, Lower row: MgO element).
Matrimid-0%-1 day Matrimid-20%-2 days Matrimid-20%-5 days Matrimid-20%-10 days
15- 90-90
30-30
20- Ag Ag
10- 60-60
20-20
10-
5- 30-30
10-10
0- 0- 0-0
0-0
150-
200- 200-
100-
100- 100-
50-
0- 0- 0-
129
Table 3.4. XPS element binding energies of the neat Matrimid membrane before and after
silver treatment for 2 days.
Element Binding energy (eV) Shift (eV)

Before treatment After treatment
C 1s 282.9 283.2 0.3
O 1s 529.8 530.0 0.2
N 1s 398.1 398.7 0.6
changes are found in the position of binding energy profile of polymer elements after
silver treatment. This might be the evidence to rules out the presence of any interaction
between polymer and silver ions. Meanwhile, XPS Ag 3d spectra of nanocomposite
membranes containing 20wt% MgO after silver treatment are shown in Figure 3.5. A
step-wise increment in intensity and area under the index peaks of Ag element can be
observed as a function of immersion time. In addition, the analytical calculations on the
XPS spectra revealed the fact that mass percentage of silver ions underwent a change
from 21.28% up to 36.96% with an increase in immersion time from 2 to 10 days.
Therefore, XPS analysis confirms that the adsorption of silver ions into the
nanocomposite membranes is mainly due to the presence of MgO nanoparticles, which is
in good agreement with the results obtained from EDX analysis.
In order to understand the mechanism(s) involved in the migration of silver ions
into the membrane, probably it is needed to focus on the possible interactions between
MgO and Ag and their interfacial organization. Interestingly, due to peculiar
characteristics of the Ag/MgO hybrid system and its technological importance in
130
composite materials and microelectronics industry, the structure and morphology of
Ag/MgO interface has been the subject of extensive studies [40]. One of the reasons is
that the surface properties of MgO is basically considered as one of the prototype systems
for studying adsorption of ionic surfaces [41]. The physical and chemical properties of
magnesium oxide are primarily governed by the source of the precursor, that is, derived
from magnesite or precipitated from brine or seawater.
×102
Matrimid+MgO (20%)+2 days silver treatment

Matrimid+MgO (20%)+ 5 days silver treatment
Matrimid+MgO (20%)+10 days silver treatment
120
Intensity (CPS)
80
40
380 376 372 368 364 360

Binding Energy (eV)
Figure 3.5. XPS Ag 3d spectra of the nanocomposite membranes with 20wt% MgO
nanoparticles after silver treatment for different immersion times.
Basically, Ag is a noble metal, and hence cannot be involved in any chemical
reaction with other materials. Therefore, the possibility of interaction in the form of
chemical adsorption between Ag ions and MgO is very low. High surface activity and
131
strong basicity characteristics of MgO surface may suggest the physisorption mechanism
for this process of Ag adsorption onto the MgO which is confirmed by other researchers
[42]. Interestingly, this mechanism is in agreement with the findings in other works. For
example, interfacial study on the Ag/MgO using cluster models has determined the
presence of electrostatic bonding rather than covalent at Ag/MgO interface [43].
Considering the Face-Centered Cubic structure of MgO crystal, three possible
sites have been proposed for the adsorption of Ag ions onto the MgO viz. above O ions,
above Mg ions, or in between the octahedral sites [44]. The majority of interfacial studies
on Ag/MgO systems have confirmed that the main attractive forces from MgO are
offered by oxygen ions rather than magnesium ions [45]. In other words, the attractive
energy between distinguished ions causes the migration of Ag cations into the
membranes and finally they are deposited onto the anionic oxygen sites. In this respect,
Figure 3.6. might be an appropriate representative model for molecular structure of
adsorption of Ag ions onto the surface of MgO nanoparticles in which preferential
adsorption sites are assigned to the oxygen atoms of MgO. This model is quite similar to
the one proposed by Qin et al.[40].
In addition, Flank et al. demonstrated by their research study that the electrostatic
attractive force between MgO and Ag is so strong that may support the Ag ion over the
range of monolayer Ag deposits, which can lead to a formation of three-dimensional Ag
clusters over the MgO surface [46]. This fact is well considered in our proposed model
132
(Figure 3.6.) and dotted lines represent the direct interaction between oxygen and silver
atoms, while dashed lines indicate the over-layer interactions.
Legend
Ag
Mg
O
Figure 3.6. The schematic representation and molecular model for the adsorption of Ag
ions onto the oxygen sites at the surface of MgO. (Type of Interaction: Direct: dotted
lines, Secondary: dashed lines)
In literature, the calculated distance for Ag-O interaction is reported to be from 2.28 to
2.70Å which is determined through ab initio method [40]. It could be seen from our
characterization results that the amount of silver ions inside the membranes shows a
gradual increase even after 5-day immersion. This may suggest that the process of Ag+
adsorption onto the MgO surface is a rate dependant process in which adsorption sites are
occupied progressively with the retention time.
133
3.3.4 Effect of silver treatment on the gas separation performance of nanocomposite
membranes
The gas permeation test was carried out on the nanocomposite membranes with
20wt% MgO content to investigate the effect of silver treatment on the gas separation
performance. The pure gas permeability and ideal selectivity of membranes treated with
silver ions are presented in Table 3.5. Results show that silver treatment for 2 days causes
a significant decrease in permeability of all gases. It is interesting to note that the gas
permeability results are in correlation with the size of gas molecules. In other words, the
permeability increases with decreasing gas kinetic diameters in the sequence of CH 4 , N 2 ,
O 2 , CO 2 , H 2 and He. Moreover, a further decrease in permeability is observed by
prolonging the silver treatment. Thus, the minimum permeability is obtained for the
nanocomposite membranes with 10 days silver treatment time. However, surprisingly, a
reverse trend is observed for the light gases (i.e., He and H 2 ) and the immersion time has
an increasing effect on permeability of the membranes toward these two gases. The direct
consequence of this strange behavior is the achievement of significantly enhanced
selectivity of light gases over nitrogen. For example, H 2 /N 2 selectivity has reached to
146, which is 70% higher than that of pure polymer membrane. Likewise, He/N 2
selectivity of the nanocomposite membrane with 10-day treatment has increased up to
twofold compared to the untreated sample membrane. It also can be found that, CO 2 /CH 4
selectivity (which is of the paramount industrial importance) reaches up to 42.3 after 10-
day silver treatment which is superior to both neat Matrimid and Ag+-untreated
nanocomposite membranes. The following hypotheses can be drawn in order to explain
the enhanced gas separation performance of membranes after silver treatment.
134
Table 3.5. The effect of silver treatment on the permeability and selectivity of Matrimid-MgO nanocomposite membranes.
Polymer matrix- Permeability (Barrer) Ideal Selectivity

MgO loading (%)-
Retention time (day)
He H2 O2 N2 CH4 CO2 H2/N2 He/N2 CO2/ CH4 O2/N2 H2/ CO2
Matrimid-20%- 0 day 31.0 32.2 2.27 0.360 0.278 8.27 89.5 86.0 29.8 6.31 3.89
Matrimid-20%- 2 days 20.7 19.8 1.28 0.183 0.130 5.13 108.2 112.8 39.4 7.00 3.86
Matrimid-20%- 5 days 23.0 22.5 1.26 0.173 0.121 5.05 129.9 132.8 41.7 7.28 4.45
Matrimid-20%- 10 days 25.9 22.7 1.17 0.155 0.102 4.31 146.5 166.9 42.3 7.54 5.26
Testing Temperature 35oC
135
As explained in previous sections, the average pore size of the MgO nanoparticles is far
larger than the size range of gas molecules and thus results in the low selectivity
performance for the gas pairs. Therefore, this phenomenon exterminates the notion of
exploiting advantageous affinity of MgO toward CO 2 for gas separation. Revitalizing the
advantageous properties of MgO for gas separation would not be possible unless some
strategies be adopted to tailor the porous structure of MgO nanoparticles and diminish the
pore sizes to the order of gas molecules. It seems that the surface coating of MgO with
multilayer silver ions provides this opportunity to perform this modification. Although,
the addition of silver ions may activate the facilitate transport role of MgO; however the
narrowed pathways for the transport of gas molecules caused by Ag layers also brings
about the size exclusion mechanism in the membranes. Therefore, one can notice from
the permeability results that positive role of facilitated transport in permeability is highly
influenced by the negative role of size exclusion mechanism. The constant decrease in
membrane permeability and increase in He/N 2 , H 2 /N 2 , O 2 /N 2 and CO 2 /CH 4 selectivity
by prolonging the treatment step clearly support the fact that the sizes of available
pathways for gas transport may be reduced to the level of gas molecule dimensions, thus
distinguishing the size difference of these gas pairs. Furthermore, presence of MgO
facilitates the transport of CO 2 while size exclusion provides more resistance for the
transport of CH 4 due to its larger kinetic diameter compared to CO 2 . As a result, the
combination of these two mechanisms results in advantageous properties of silver treated
nanocomposite membranes for CO 2 /CH 4 separation.
136
It is worthwhile to note that the presence of Ag ions inside the membranes may
also affect the transport properties of gas molecules within the membrane. However,
despite the abundance of studies on the interaction between olefins with silver ions,
interestingly, little work has been done about the interaction of silver ions with CO 2 and
other gases used in this study. In agreement with other reports [47], it can be concluded
that the gas transport properties of silver doped nanocomposite membranes is governed
by the combination of solution-diffusion (in the polymeric medium), size exclusion (in
the silver coated porous structure of MgO), and facilitated transport mechanisms (by
interaction with MgO and/or Ag). However, the latter is only effective for the transport of
CO 2 .
The sorption isotherms of CO 2 gas in the nanocomposite membranes before and
after Ag treatment are shown in Figure 3.7. It can be seen that sorption behaviors abide
the dual-mode sorption model and the sorption capacity of nanocomposite membrane has
been decreased after doping with silver ions. It is known that MgO has the capability to
presents both reversible and irreversible affinity toward CO 2 through interaction with
oxygen sites of MgO. The irreversible adsorption of CO 2 onto the MgO sites can reduce
the permeability of CO 2 . It was shown that upon doping, Ag ions interact strongly with
oxygen sites. Therefore, it seems there remain far less available sites for CO 2 molecules
to be adsorbed onto the MgO surface since the surface sites of MgO is already occupied
with Ag ions. As a result, it is reasonable to observe less sorption values for CO 2 in
Mat+MgO+Ag membranes compared to the sample without Ag and the results already
137
corroborate this fact by showing the decline in the sorption values of
Matrimid+MgO+Ag.
45
C [cm3(STP)/cm3(membrane)] 40
35
30
25
20
15
10
Mat+MgO(20%)
5 Mat+MgO(20%)+Ag(10 days)
0
0.0 5.0 10.0 15.0
P [atm]
Figure 3.7. CO 2 sorption isotherms for the nanocomposite membranes before and after
silver doping.
The transport of CO 2 may be affected by MgO and/or Ag. The enhanced transport
of CO 2 due to the presence of Ag proposed in this study is in accordance with the recent
study [47] in our group indicating the facilitated transport of CO 2 molecules. Considering
the case of MgO, it was indicated that MgO has the ability to interact electrostatically
over multilayers, so there might be the possibility that MgO nanoparticles interact with
CO 2 molecules passing over the Ag layer and enhance the transport of CO 2 molecules.
Therefore, one may also consider that the presence of Ag coated MgO nanoparticles
throughout the membrane may provide a driving force for the transport of CO 2 gas
138
molecules. Although it is difficult to quantitatively provide a measure for the phenomena,
but we deem it is better not to totally rule out the possibility of presence of facilitated
transport caused by MgO and/or Ag along with other obvious separation mechanisms
introduced.
Structural analysis of the silver-treated membranes by XRD validated our
hypothesis about the microstructural changes and role of size exclusion mechanism after
silver treatment. Figure 3.8. shows the XRD spectra of membranes before and after silver
treatment. It can be seen that almost no peak shift was occurred in the spectra of the
3000
2.36 Å Pure Matrimid

Matrimid+MgO(20%)
2500
Matrimid+MgO(20%)+2 days silver treatment
2000
Intensity
1500
3.78 Å 2.04 Å
1.44 Å
1.23 Å
1000
1.179 Å
500
0
5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85
2 Theta (degree)
Figure 3.8. The XRD spectra of the membranes before and after silver treatment with
different profiles.
139
polymer after silver treatment. This implies that the d-spacing of the polymer matrix has
almost remained unchanged. However, analysis of the spectra shows that some new
peaks have been appeared by incorporation of nanoparticles which can be ascribed to the
crystalline structure of MgO particles. These peaks are distributed in the region between
1.179 to 2.36 Å. It is clearly depicted that the silver treatment has further altered the
morphology of the membranes. In fact, after a 2-day silver treatment, the intensity of
these peaks tended to increase and the maximum values were obtained for the membranes
with 10-day treatment period. Since the location of the peaks remains unchanged, the
intensity increase observed for the peaks may indicate the growth of the crystalline
structures at the vicinity of MgO nanoparticles. It also seems that attractive force between
silver cations and oxygen anions promote the integrity of the whole structure around the
nanoparticles. These results further corroborate our hypothesis on the development of
finer pathway for the gas transport through the membranes which brings about the
stronger size exclusion effect to the system.
3.4 CONCLUSIONS
Flat nanocomposite membranes were fabricated by the introduction of magnesium
oxide nanoparticles into the Matrimid polymer matrix. The increment in the gas
permeability as a function of particle content and the drop in gas selectivity reflected the
fact that the average pore size of MgO (30 Å) is much larger than the kinetic diameters of
gas molecules. The heat treatment at high temperatures followed by quenching resulted in
the highest gas permeability while retaining selectivity. This was ascribed to the increase
140
in fraction of free volumes in the polymeric medium of membrane structure. Silver
treatment was carried out in order to tailor the performance of membranes. XPS and EDX
analyses revealed that in contrast to the polymer, it is MgO nanoparticles that attract the
silver ions, thus resulting in the penetration of Ag cations into nanocomposite membranes
followed by adsorption onto the surface of MgO nanoparticles. The amount of adsorption
was monotonically increased with the retention time. It is found that silver treated
nanocomposite membranes exhibit better gas separation performance for all gas pairs and
H 2 /N 2 and CO 2 /CH 4 selectivity of nanocomposite membranes after 10-day silver
treatment were about 146.5 and 42.3, respectively. The role of silver ions was recognized
to be covering the porous structure and control of the pore size of MgO nanoparticles. As
a result, in addition to the solution-diffusion mechanism, the size exclusion mechanism at
MgO-Ag+ structures as well as the presence of facilitated transport due to special
interaction between CO 2 and MgO were suggested by experimental analyses to be the
governing mechanisms in the superior separation performance of the newly developed
Matrimid-MgO-Ag+ nanocomposite membranes.
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147
CHAPTER FOUR
HYDROGEN SEPARATION AND PURIFICATION IN MEMBRANES OF
MISCIBLE POLYMER BLENDS WITH INTERPENETRATION NETWORKS
4.1 INTRODUCTION
Hydrogen is anticipated to play an inevitable role as one of the promising sources
of energy in the future. According to the latest statistics, the U.S. annual production of
hydrogen is appraised to about 9 million tons [1]. The major proportion of produced
hydrogen is used to supply the refinery and fertilizer industries. The constant increasing
demand for highly purified hydrogen has resulted in attracting more attentions for
extensive research studies on advancement of the technologies for generation of
hydrogen with higher efficiency and lower production cost.
At present, steam reforming of hydrocarbons is predominantly the established
technology for generation of hydrogen and it supplies about half of the world’s demand
for this viable gas. In this process, a stream of natural gas mainly composed of methane
undergoes a water gas shift reaction. The yield product has to be further processed in a
separation process in order to remove unwanted carbon dioxide and other by-products
from the mixtures with hydrogen. Currently, commercially available separation processes
148
for this purpose are pressure swing adsorption, amine absorption and absorption using
aqueous solution of potassium carbonate which are highly energy intensive [2-4].
Membranes have received global attention as a promising technology for gas
separation and purification. This mainly stems from the small footprint, reliability,
considerable high energy efficiency and low capital cost offered in membranes compared
to other conventional separation processes [5,6]. It is also worth noting that hydrogen
recovery has been among the first commercial applications of membranes in the field of
gas separation [7]. The major application of membranes for hydrogen separation includes
hydrogen purifications, fuel cell technology and membrane reactor processes [8].
Recovery of hydrogen from hydrocarbon streams, recovery of hydrogen from ammonia
streams, adjusting the composition of hydrogen in synthetic gases are among the major
industrial and petrochemical applications of hydrogen purification [9]. Interestingly,
membrane separation systems have good potentials for integration with hydrogen
generation equipments that permits the processes to be entirely carried out in a single
processing unit.
In recent years, research directions have been on both inorganic and organic
materials to develop membranes with desirable hydrogen separation properties. There are
different approaches for the use of inorganic membranes in hydrogen separation. One is
based on a dense metal layer deposited on a ceramic support. In this category, palladium-
based membranes are more attractive and generally exhibit high hydrogen permeability
and selectivity [10]. Zhang et al. [11] studied the hydrogen permeation behavior of dense
149
palladium membranes prepared by microfabrication technique. According to their study,
this technique offers high durability to membrane for operation in elevated temperatures.
The application of other metals also has also been examined. For example, Ernst et al. [8]
successfully fabricated a nickel/ceramic composite membrane which possesses high
permeability and selectivity to hydrogen. However, inorganic membranes are fraught
with complexities in fabrication, difficulties in prediction of membrane permeation
properties and generally require high operating costs [12].
On the other hand, the advantageous properties of polymeric membranes like ease
of processing and appropriate robustness may dominate the application of organic
membranes over inorganic counterparts. However, the main drawback of polymeric
membranes for hydrogen separation compared to inorganic is the operating temperature
range that can be used. The coincidence of unfavorable diffusivity selectivity and
solubility selectivity for selected gas pairs like H 2 and CO 2 has also restrained the
application of polymeric membranes for separation of such molecules. This mainly stems
from the negligible difference in kinetic diameters of gas molecules. Swelling of the
interstitial spaces between polymer chains due to penetrant-induced plasticization may
also play a part which restrains the performance of separation based on size exclusion
mechanism [13]. It is well shown that CO 2 induced plasticization severely deteriorates
the separation properties of membranes prepared from glassy polymers including
polyimides [14]. The presence of challenges has resulted in limited number of reports on
the development of polymeric membranes for hydrogen separation. In a recent research
study in our group [15] polymeric membranes were successfully fabricated with high
150
selectivity for H 2 /CO 2 . It was observed that chemical surface modification of 6FDA-
durene offers membranes with gas selectivity of over 100 for H 2 /CO 2 in pure gas tests
and about 42 in mixed gas tests.
The objective of this study is to fabricate high performance polymeric membranes
suitable for separation and purification of hydrogen. Dense flat membranes were
fabricated using the solution blending technique using Matrimid and PBI. Matrimid is a
polyimide with high gas permeability and selectivity, high thermal stability and solvent
resistance [16-17]. Similarly, PBI is a high performance polymer possessing high glass
transition temperature, outstanding thermal stability and chemical resistance that makes it
suitable candidate for advanced technologies like fuel cells [18-20]. The gas permeation
characteristics of Matrimid /polybenzimidazole (PBI) homogenous blend membranes are
evaluated. The effects of composition on miscibility, microstructure and gas separation
performance of membranes are also investigated. Gas separation performance of
membranes was further ameliorated through chemical cross-linking modification of blend
constituents using distinct types of cross-linking agents. To our best knowledge, this is
the first study focusing the exploitation of unique properties of blending high
performance polymers of Matrimid and PBI for the development of specialty membranes
for hydrogen separation and purification.
4.2 EXPERIMENTAL
4.2.1 Materials
151
The polyimide (Matrimid5218) (3,3’,4,4’-benzophenone tetracarboxylic
dianhydride and diamino-phenylindane) was purchased from Vantico Inc., (Luxemburg)
and poly [2,2’-(1,3-phenylene)-5,5’-bibenzimidazole] (PBI) was obtained from Aldrich
Chemical Company Inc. (Milwaukee, USA). Both polymer powders were dried for
overnight at 120oC under vacuum prior to use. The chemical structure of polymers is
shown in Figure 4.1. N-methyl-2-pyrolidone (NMP) and methanol were supplied by
Merck and used as solvent for polymers. Cross-linking agents used in this study were p-
xylenediamine and p-xylenedichloride which were supplied by Merck, (Germany) and
TCI Inc., (Japan), respectively. Ethanol (analytical grade) was supplied by Merck and
was used for density measurements.
Matrimid
PBI
Donor: C=O (Matrimid)

Acceptor: N-H (BPI)
Figure 4.1. Schematic representation of the hydrogen bonding interaction between
functional groups of Matrimid and PBI.
152
4.2.2 Preparation of dense flat membranes
Polymer solutions (2 wt.% polymer/ 98 wt.% NMP) with various compositions of
25/75, 50/50, 75/25 wt% were prepared from Matrimid and PBI. Firstly, PBI with
stipulated quantity was dissolved in NMP at 150°C using a magnetic stirrer and it took
about 2 days to obtain a complete dissolution. The polymer solution was filtered using a 2
μm filter to eliminate any undissolved polymer and dusts. Subsequently, Matrimid
powders were added and stirring was continued for few days to allow the complete
mixing of blend constituents. After degassing, polymer solutions were poured onto a
silicon wafer surrounded by a metal ring. The wafers were placed in a vacuum oven and
the temperature of oven was set to 100 °C to allow slow evaporation of NMP. This
process was continued for about five days. While still under vacuum, the temperature was
gradually increased at the rate of 20 °C/0.5 hr up to 250 °C and membranes were kept at
the final temperature for overnight to assure the residual solvent removal. The as-cast
membranes were collected after natural cooling down.
4.2.3 Chemical modification of membranes
Round-cut pieces of membranes underwent cross-linking using a simple dipping
method. A 10 wt.% solution of p-xylenediamine in methanol was prepared which was
aimed for cross-linking of the polyimide. On the other hand, a solution composed of 2
wt.% p-xylenedichloride in methanol was used to cross-link PBI components.
Membranes were immersed in the solutions for stipulated periods of 5 and 10 days. After
taking out, membranes were immersed in fresh methanol to wash out unreacted
molecules followed by drying in vacuum oven at 120 °C for overnight.
153
4.2.4 Characterization techniques
The miscibility of membrane constituents was examined using differential
scanning calorimetry (DSC). Glass transition temperature (T g ) of polymer films was
evaluated on a Perkin-Elmer, DSC-Pyris 1 calorimeter. Approximately 5-10 mg of
membrane was put in aluminum pans. Two consecutive scans from 50 to 450 °C at the
heating rate 10 °C/min were performed for each sample. The T g of samples was
determined as mid-point transition temperature of the second scan.
A standard displacement technique was employed to measure the density of blend
films [21]. Round pieces of films were punched and weighed in air ( wair ) and then in
ethanol ( wEtOH ), respectively. The density of polymer film was calculated using the
following equation:
wair
ρ polymer = ρ EtOH (4.1)
wair − wEtOH
where ρ EtOH is the density of ethanol. Five pieces of films were prepared for each
sample.
The structural properties and inter-chain spacing of membranes were analyzed
qualitatively on an X’Pert PRO-MRD wide-angle X-ray diffractometer (XRD) from
PANalytical. The measurements were carried out by using Cu Kα radiation with a
wavelength of λ = 1.54 Å at room temperature. The scan range was from 4 to 70

˚ with a
step increment of 0.04̊/s. Average d-spacing was determined based on the Bragg’s law,
viz.
154
nλ = 2d sin θ (4.2)
the intersegmental spacing between two polymer chains and θ indicates the diffraction
angle.
Molecular simulation was performed using the Amorphous Cell procedure
developed by Material Studio software packages, Accelrys Inc. The most stable
energy-minimized configurations of polymer chains were simulated to qualitatively
examine the possible chain morphology for crosslinking.
4.2.5 Gas permeability measurements
The gas permeation properties of membranes were determined by a variable-
pressure constant-volume method. Detailed experimental design and procedures can be
found elsewhere [22]. The rate of pressure increase (dp/dt) at steady state was used for
the calculation of gas permeability with the following relationship:
273.15 × 1010 Vl  dp 
P=   (4.3)
760 AT (( P0 × 76) / 14.7)  dt 
where P is the gas permeability of a membrane in Barrer (1Barrer = 1×10-10 cm3 (STP)-
operating temperature (K) and the feed gas pressure in the up-stream is given by P 0 in
psia.
The pure gas permeability was obtained in a sequence of H 2 , N 2 , CH 4 and CO 2 at
35 °C for each piece of membrane. The H 2 permeability test was conducted at 3.5 atm,
155
while the testing pressure for other gases was 10 atm. The ideal selectivity of a membrane
for gas A to gas B was evaluated as follows:
PA
α A/ B = (4.4)
PB
The apparent diffusion coefficient (D app ) is obtained by using time-lag (θ) method as
follows:
L2
Dapp = (4.5)
6θ
where in this expression, θ is the diffusion time-lag. The apparent solubility coefficient
(S app ) was subsequently calculated through the following expression:
P
S app = (4.6)
Dapp
4.3.1 The miscibility and other characteristics of blends
Extensive studies have given countenance to the marked role of constituents’
compatibility on the phase morphology and consequently gas separation performance of
blend membranes [23]. Hence, it is well accepted that miscibility analysis should be set
as a prerequisite in the design of superior gas separation membranes. The miscibility of
polyimides and PBI has been the subject of few studies [18,24-26]. All these reports
unanimously corroborate the miscibility of these polymer pairs. However, referring to
those reports, either the analyses have been carried out in a limited range or the grade of
materials is found to be different from what was used in this study. Therefore, the
156
miscibility of as-cast blend membranes was examined over the various ranges of
compositions. Obtaining clear and transparent films and the presence of a single T g in
calorimetry thermograms have been verified to be appropriate indicatives of miscibility
in the molecular level. All the films prepared from the blends of Matrimid and PBI were
transparent and homogenous and no symptom of phase separation was detected by visual
observation. The DSC thermograms of the blend membranes with various compositions
are depicted in Fig. 2. These results also confirm the miscibility of blends by showing the
presence of composition dependent single T g that all fall in the midst of each individual
components’ T g value. In addition, a positive shift in T g was observed with an increase
in PBI composition which was in fact due to the higher T g of PBI.

Heat Flow (mW)
b
c
d
e
300 330 360 390 420 450

Temperature (C)
Figure 4.2. DSC thermograms of the polymer blend membranes and individual
constituents. (a) 0, (b) 25, (c) 50, (d) 75, (e) 100 wt% PBI composition.
The glass transition temperature of polymer blends was calculated theoretically by using
the Fox equation which is expressed as follows:

157
1 W1 W2
= + (4.7)
Tg Tg Tg
1 2
In this Eq., T g1 and T g2 are glass transition temperatures (K) of individual polymers while
W1 and W 2 indicate mass fractions of each component in the blend.
The T g -composition curve of blend system is shown in Figure 4.3. It can be seen
that the connection of experimental data points forms a sigmoidal curve. The comparison
of experimental and theoretical results indicate that the Fox equation can almost
successfully predict the T g values for the blends rich in Matrimid. However, the trend is
followed by a negative deviation in prediction of T g as the composition of PBI is further
increased. Interestingly, the deviation turns to the positive prediction once the
composition of PBI in the blend system exceeds 65 wt.%. It should be noted that
deviation from the theoretical results is a common phenomenon which is seen in behavior
of majority of polymer blends and is generally a reflection of the specific interactions
between the components. The nature of miscibility of Matrimid/PBI is believed to be the
intense hydrogen bonding between N-H group of PBI and C=O group of Martimid which
provides a specific interaction for intermolecular compatibility [18, 24-25]. This strong
interaction has been confirmed by various techniques including FTIR where Karasz et al.
[27] observed shifts in N-H bond of PBI and carbonyl group of Matrimid. The schematic
representation of this interaction is shown using dashed lines in Figure 4.1.
4.3.2 Gas separation characteristics of blend membranes
Basically, potential use of polymeric blends for the transport and separation of
gaseous systems entails a dexterous control over the phase morphology and interfacial
158
interaction of blend components [28-29]. The confirmed miscibility may satisfy this
prerequisite criterion for the use of Matrimid/PBI blends for gas separation. Table 4.1.
tabulates the results of gas permeability measurements and ideal selectivity of blend
membranes. The results denote a general decline in gas permeability with an increase in
PBI concentration.
440
420 Experimental
Theoretical-Fox Eq.
400
380
Tg
360
340
320
300
0 20 40 60 80 100
Matrim id Com position (%)
Figure 4.3. Composition dependency of T g and comparison with theoretical values
predicted by Fox equation.
It can be found that the decrease in gas permeability of membranes commensurate
with kinetic diameter of gas molecules. In other words, gases with larger kinetic diameter
experience more decrease in permeability with the increase of PBI content. The
instrumental consequence of this behavior was the melioration in selectivity of selected
gas pairs. For example, data in Table 1 show that the selectivity of H 2 /CO 2 and H 2 /N 2
159
increases by about 1.5 fold and reaches to about 9.43 and 260.47, respectively.
Interestingly, quite similar improving trend was observed in the selectivity of CO 2 /CH 4
which there is a minor difference in size of these molecules and ideal selectivity of this
gas pair was reached to about 60. It is worthwhile to mention that the separation of this
gas pair is of paramount importance in processing of natural gas and considering the large
amount of production, any small improvement in efficiency of the process could result in
substantial cost reduction in processing of natural gas.
Table 4.1. The permeability and ideal gas selectivity of polymer blend membranes with
various compositions.
Membrane Permeability (Barrer) Ideal Selectivity

constituents
H2 N2 CH4 CO2 H2/N2 H2/ CO2 CO2/ CH4
Matrimid®5218 27.16 0.280 0.210 7.00 97.00 3.88 33.33
Matrimid/PBI(75/25%) 19.72 0.163 0.130 4.19 120.98 4.07 32.23
Matrimid/PBI(50/50%) 13.06 0.072 0.045 2.16 181.38 6.05 48.00
Matrimid/PBI(25/75%) 5.47 0.021 0.0097 0.58 260.47 9.43 59.79
PBIa 0.6 0.0048 0.0018 0.16 125 3.75 88.88

Testing Temperature: 35ºC
a From reference [34]
The gas selectivity of a membrane for a gas pair is the ratio of their individual
permeability coefficients, while the gas permeability (P) is a product of solubility (S) and
diffusivity (D) coefficients which are highly dependent on the nature of penetrant and the
membrane material and morphology. These coefficients jointly control the overall
permeability of a membrane. Table 4.2 provides the calculated values of the diffusivity
160
and solubility coefficients of the membranes developed in this study. It seems that the
interrelation between the size of gas molecules and changes in permeability as well as the
presence of interaction between the components fortify the idea that the possible reason
for changes in transport properties of membranes might have been the effect of PBI on
membranes morphology in a molecular level. Based on the solution-diffusion
mechanism, the present experimental results imply that the incorporation of PBI results in
the enhanced stiffness and decreased spacing between polymer chains with little changes
in solubility selectivity. In addition, it is well documented that free volume is a
determining factor in gas transport properties of a membrane [30-31].
Table 4.2. Gas diffusion coefficients and solubility coefficients of polyimide, blend
membranes and modified blend membranes.
D (×10-8 cm2/s) S (×10-2 cm3(STP)/cm3 cmHg)

Membrane constituents
H2 N2 CH4 CO2 H2 N2 CH4 CO2
Matrimid®5218 174.0 0.413 0.093 0.897 0.16 0.68 2.26 7.80
Matrimid/PBI (75/25%) 136.0 0.312 0.061 0.572 0.15 0.52 2.12 7.32
Matrimid/PBI (50/50%) 94.0 0.144 0.022 0.311 0.14 0.50 2.03 6.95
Matrimid/PBI (25/75%) 44.5 0.044 0.005 0.088 0.12 0.48 1.85 6.62
Matrimid/PBI (25/75%)-5 days PXDC 43.8 0.040 0.009 0.070 0.12 0.47 1.87 6.50
Matrimid/PBI (25/75%)-10 days PXDC 33.9 0.030 0.008 0.048 0.12 0.46 1.86 6.41
Matrimid/PBI (25/75%)-5 days PXDA 34.4 0.032 0.003 0.034 0.12 0.47 1.82 6.13
Matrimid/PBI (25/75%)-10 days PXDA 32.1 0.029 0.002 0.023 0.11 0.46 1.81 6.22
Therefore, the free volume analysis was performed in order to investigate the effect of
incorporation of PBI on microstructure and how the strong interaction between blend
components can alter the transport properties of membranes.
161
The fractional free volume (FFV) calculations were based on following equations:
Vsp − V0
FFV = (4.8)
Vsp
V0 = 1.3VW (4.9)
Vsp = 1/ ρ (4.10)
where Vsp is the specific volume of polymer film (cm3/g) and V0 is the volume occupied
by the chains (cm3/g). The values of Van der Waals volumes (V W ) for individual
polymers were obtained by applying group contribution method [32]. According to Bondi
[33], Eq. (9) provides a good approximation for the evaluation of V0 based on the Van
der Waals volume. Moreover, ρ represents the density (g/cm3) of polymer films which
was measured experimentally. The corresponding values of V W and M for blends were
calculated using the mixing rules. The results of measurements and calculations are
shown in Table 4.3. Data in this table indicate that Matrimid and PBI possess the
maximum (0.268) and the minimum (0.116) fractional free volumes, respectively. These
values are in good agreement with other reports [14, 34]. The difference in FFV of these
materials possibly stems from the difference in chemical structure [30]. It can be seen
from Figure 4.1. that Matrimid and PBI are quite similar in structure of backbone and
repeating unit. However, it is expected that the presence of few side oxygen groups as
well as large methyl groups in the structure of Matrimid does not allow the polymer
chains to come closer. Furthermore, molecular simulation is found to be a very useful
tool in analysis of the properties of membranes [35].
Application of molecular simulation study on the configuration and
conformations of polymer chains corroborated our hypothesis. As it is presented in Fig. 4,

162
clearly a better chain packing can be observed between the PBI macromolecules.
However, in contrast to PBI, there exists a relatively larger free volume formed in the
structure of Matrimid chains which mainly occurs in the junction of two repeating units
where the bulky methyl groups provide spatial hindrance against well chain packing.
Table 4.3. The effect of blend composition on the physical properties and fraction of free
volume of membranes.
Membrane constituents M (g/mol) ρ (g/cm3) Vw (cm3/mol) V0 (cm3/g) Vsp (cm3/g) FFV
Matrimid®5218 568.6 1.172 273.1 0.624 0.853 0.268
Matrimid/PBI (75/25%) 469.5 1.192 229.9 0.637 0.839 0.241
Matrimid/PBI (50/50%) 399.6 1.244 199.6 0.649 0.804 0.193
Matrimid/PBI (25/75%) 347.9 1.274 177.1 0.662 0.785 0.157
PBI 308 1.311 159.8 0.674 0.763 0.116
It should be noted that intensity of this hindrance is large enough that results in
the chain conformational rotation at the junction of repeating units in the structure of
Matrimid. Therefore, in consistence with data in Table 4.1., the FFV of membranes films
undergoes a stepwise decline by an increase in PBI composition. It should be noted that
in addition to this phenomenon, the formation of strong hydrogen bonding between blend
components which was not present in any of individual polymers may also contribute to
the diminishment of FFV by keeping the distinct polymer chains in the minimum
interstitial distances. This hydrogen bonding also restrains the polymer chain from free
rotation and mobility. The augmentation of glass transition temperature by increasing in
PBI composition is a sign of enhancing chain stiffness. The increase in density as a result
163
of increase in the PBI content in the blend membrane can be considered as another
evidence for amplified polymer chain packing throughout the microstructure of resultant
membranes.
(a)
(b)
Formation of free volume at the

junction of two repeating units
Figure 4.4. Analysis and comparison of the status of free volume in the structure of (a)
PBI and (b) Matrimid membranes using molecular simulation.
The XRD analysis was performed in order to obtain further information about the
effects of blending on microstructure and d-spacing of membranes. As shown in Figure
4.5, the indicative peak of Matrimid is a merger of two amorphous peaks with d-spacings
of 3.86 and 5.53 Å. An increase in PBI concentration gradually vanishes the peak of
Matirmid at 5.53 Å and finally the sample containing 75 wt.% PBI possesses almost a
mere peak at 3.86 Å. The shift in d-spacing indicates a shift of interstitial chain-chain
distance and free volume distribution toward a tighter and narrower structure. The results
164
of microstructural analysis of polymer blends indicate that the decrease in permeability
and enhancement in gas separation performance can be attributed to the contribution of
reduction in fractional free volumes and d-spacings, restrictions in mobility of polymer
chains and increase in chain packing density.
2000
1800
Matrimid/PBI (75/25)
1600 3.86 Å Matrimid/PBI (50/50)
Matrimid/PBI (25/75)
1400
Pure Matrimid
1200 5.53 Å
Intensity
1000
800
600
400
200
0
4 14 24 34 44 54 64
2 Theta (degree)
Figure 4.5. The XRD spectra of blends depicting the effect of composition on
microstructure of membranes.
These changes highly affect the diffusivity selectivity and stabilize the membrane
structure against CO 2 -induced swelling phenomena and consequently result in significant
increment in selectivity for H 2 /CO 2 , H 2 /N 2 , and CO 2 /CH 4 gas separation. In fact, one of
the main advantages of developed blend membranes in this study is exploiting benign
properties of PBI for gas separation that otherwise could not be fabricated as a free-
standing membrane due to its poor processibility and high degree of brittleness.
165
4.3.3 Effect of chemical modification on performance of membranes
Abundance of reports [16, 36-38] on the successful improvement of gas
separation performance of chemically modified polymeric membranes initiated the idea
of applying this technique in this study. The presence of five carboxyl group in repeating
unit of Matrimid and two N-H groups in repeating unit of PBI provides a great potential
that these polymers easily be involved in any modification reactions. Thus, Matimid/PBI
blend membranes with composition of (25/75 wt.%) which exhibited the superior
performance to other compositions were chemically modified using two different cross-
linking agents. The proposed mechanisms for cross-linking process are shown in Figures
4.6. and 4.7. Moreover, the most stable energy-minimized configurations for cross-linked
PBI and Matrimid are also illustrated in these figures. According to these schematics, in
the course of chemical modification, p-xylenedichloride molecules attack to the N-H
groups of PBI and p-xylenediamine molecules react with amide groups of Matrimid.
Obviously, it seems that the chemical structure of Matrimid contains a polar bond (ether
groups) which may result in lesser linearity of the polymer backbone as well as a lesser
degree of molecular packing compared to the PBI structure. The chemical modification
of polyimides [36-37] and specifically Matrimid [16] using p-xylenediamine have been
extensively investigated and verified. Similarly, the successfulness of chemical
modification of PBI with p-xylenedichloride through this mechanism was previously
confirmed in our group where Wang et al. [39], employed FTIR and XPS techniques and
confirmed the cross-linking of PBI membranes post-treated for up to 24 hrs. Therefore, it
is anticipated that the reaction starts with modification of functional groups at the
outermost surface of membranes which are easily accessible to the cross-linking agents.
166
(a)
(b) (c)
(c)
Figure 4.6. (a) Proposed mechanism for the chemical cross-linking modification of
Matrimid component of blend using p-xylene diamine. (b) Chemical structure of p-xylene
diamine, (c) possible chain morphology and configuration of p-xylene diamine cross-
linked Matrimid. (cross-linking agents are specified by circles).
In the meantime, swelling of membranes structure by the carrier (i.e., methanol) provides
the opportunity for the transport of the cross-linking agents to penetrate inside the
membranes and access the functional groups of polymers within the membrane structure.
The process of cross-linking at the internal structure of membrane is expected to decline
with the progress of superficial modification which seems to impede further inward
penetration of agents.
167
(a)
(b) (c)
Figure 4.7. (a) Proposed mechanism for the chemical cross-linking modification of PBI
component of blend using p-xylene dichloride. (b) Chemical structure of p-xylene
dichloride, (c) possible chain morphology and configuraion of p-xylene dichloride cross-
linked PBI. (cross-linking agents are specified by circles).
Gas permeability and ideal gas selectivity of modified membranes with p-
xylenedichloride and p-xylenediamine are presented in Tables 4.4. and 4.5., respectively.
It can be seen from the results that chemical modification of membranes clearly affects
the gas permeability of membranes and a gradual decline in gas permeability was resulted
by prolonging the immersion time. Interestingly, the extent of depletion in permeability
follows the similar trend of dependence to the size of gas molecules as it was observed in
permeability of blend films. Consequently, this characteristic phenomenon results in
variation in selectivity performance of membranes.
168
Table 4.4. The effect of chemical modification using p-xylenedichloride on gas
permeability and selectivity of blend membranes.

constituents

Matrimid®5218 27.16 0.280 0.210 7.00 97.00 3.88 33.33
Matrimid+PBI(25/75) 5.47 0.021 0.0097 0.580 260.47 9.43 59.79
Matrimid+PBI(25/75)
5.34 0.019 0.0175 0.453 281.05 11.79 31.03
duration= 5 days
Matrimid+PBI(25/75)
4.04 0.014 0.0158 0.306 288.57 13.02 19.36
duration= 10 days
Table 4.5. The effect of chemical modification using p-xylenediamine on gas
permeability and selectivity of blend membranes.

constituents
Matrimid®5218 27.16 0.280 0.210 7.00 97.00 3.88 33.33
Matrimid+PBI(25/75) 5.47 0.021 0.0097 0.580 260.47 9.43 59.79
Matrimid+PBI(25/75)
4.09 0.0152 0.0046 0.209 269.1 19.56 45.43
duration= 5 days
Matrimid+PBI(25/75)
3.60 0.0132 0.0031 0.138 271.2 26.09 44.51
duration= 10 days
According to Table 4.4., slight improvements were achieved in selectivity of
H 2 /N 2 and H 2 /CO 2 after cross-linking of PBI, but the selectivity of CO 2 /CH 4 underwent
a slight decrease. On the other hand, as shown in Table 4.5., a similar declining trend is
169
observed for the membranes upon cross-linking of Matrimid phase. Considering the
structural models provided in Figures 4.6. and 4.7. and the results in Table 4.2., the
opposite trends in the selectivity of gas pairs upon cross-linking can be attributed to the
combinatory effects the configuration changes in the polymeric structure of membranes
as well as the inherent molecular size difference of gas molecules.
A comparison of the results in Tables 4.4. and 4.5. for the corresponding
chemically modified membranes reveals the fact that treatment with p-xylenediamine has
spelled greater effect on the transport properties of membranes noticed from the level of
changes in permeability values. As a result, the H 2 /CO 2 selectivity of the resultant
membrane has reached up to about 26 after 10 days modification with p-xylenediamine
which is considerably higher than that of other samples and corresponding individual
components.
The effect of chemical cross-linking on gas permeability decay of membranes is
probably due to the tighter interstitial spaces among the chains and restriction in vibration
and mobility of polymer chains and side groups attached to the backbone. As a result, the
diffusion of penetrant gas molecules through the membrane is hindered and gas
permeability decreases. Therefore, in agreement with a similar report [37], the enhanced
selectivity performance of membranes is mainly achieved by the diffusivity selectivity of
membranes. This was confirmed by examination of the d-spacing between the polymer
chains through XRD analysis. According to Figure 4.8., upon cross linking, the
interstitial space between the polymer chains shifted from the original value of 3.86 Ǻ
170
2000
1800 Matrimid/PBI (25/75)

3.86 Å
3.36 Å X-link-PXDC-5 days
1600 X-link-PXDC-10 days
X-link-PXDA-5 days
1400
X-link-PXDA-10 days
1200
Intensity
1000
800
600
400
200
0
4 14 24 34 44 54 64
2 Theta (degree)
Figure 4.8. The XRD spectra of blend membranes cross-linked with p-xylene dichloride
(PXDC) and p-xylenediamine (PXDA) for different periods of time.
down to minimum 3.36Ǻ after cross -linking with p-xylenediamine for 10 days. The
order of shift is proportional to the period of modification and it is more pronounced for
samples modified with p-xylenediamine. Furthermore, the molecular modeling of the
systems show that cross-linking of Matrimid results in relatively more compact structure
compared to that of PBI. It seems that bond breaking reaction at the imidazole sites of
Matrimid during the cross-linking provides this flexibility for polymer chains to find
better configuration. However, this phenomenon is not observed for cross-linking of PBI
due to its relatively rigid polymer structure. As a result, the cross-linking agent seems to
act as a bridge between the lateral polymer chains.
171
Furthermore, it is anticipated that cross-linking of polymer chains offers a special
integrity and structural stability which protects the membrane from CO 2 induced swelling
and plasticization. One possibility is that more intense influence of cross-linking with p-
xylenediamine compared to p-xylenedichloride might be due to difference in
concentration of the cross-linking agents in the solution. This also could be ascribed to
the difference in activity of functional groups of constituents towards corresponding
cross-linking agents. In such a case, results may indicate that the cross-linking efficiency
of Matrimid is considerably higher than that of PBI.
It seems also worthwhile to consider this issue with respect to the size of the
crosslinking agents. Structural analysis of p-xylenedichloride and p-xylenediamine by
molecular simulation denotes the fact that while these chemical agents have similar
molecular width (around 3Ǻ measured by Material Studio software), there is only a minor
molecular length different between these two cross-linking agents, (7.9 and 8.0Ǻ, f or p-
xylenedichloride and p-xylenediamine respectively). In Fig.9, the structure and
configuration of the cross-linking agents are provided at the minimum energy. According
to this figure, it can be seen that except the benzene group that both cross-linking agents
have in common, the rest of the molecules have not much difference in the spatial
configuration. As a result, the difference in the size of these molecules is not large
enough to be considered into the account to justify about the penetration of these
molecules into the membrane structure.
172
(a) H H
C C H
N H N
H C C
H
H C C H
H H
(b) H H
C C H
H
Cl C C C C Cl
H C H
C
H H
Figure 4.9. Molecular simulation analysis of chemical structure of cross-linking agents
(a) p-xylenediamine (b) p-xylenedichloride
4.4 CONCLUSIONS
Blend membranes prepared from Matrimid and PBI are completely miscible in
the whole range of compositions in molecular level. This property is given to the blends
by strong hydrogen bonding interaction among the functional groups of components.
Therefore, incorporation of PBI resulted in improvements in gas separation performance
of Matrimid which was caused by increase in chain packing density and hindrance in
segmental mobility of polymer chains and its consequence effects on diffusivity
selectivity. This was confirmed by analysis of microstructure of membranes. Chemical
modification was found to be an instrumental means for tailoring performance of
membranes for separation of selected gas pairs. However, distinguished behaviors were
173
observed from the membrane toward cross-linking agents. The effect of p-xylenediamine
in progressive performance of membranes was more pronounced compared to p-
xylenedichloride. The Matrimid/PBI (25/75 wt.%) blend membrane cross-linked with p-
xylenediamine exhibits the best performance with H 2 /CO 2 selectivity of about 26 which
was due to high chain packing density and restrictions in segmental mobility of polymer
chains.
4.5 REFERENCES
[1] Today’s Hydrogen Production Industry, Website of U.S. Department of Energy,
http://www.fossil.energy.gov/programs/fuels/hydrogen/currenttechnology.html
[2] A.L. Kohl, R. Nielson, Gas purification, (5th ed.), Gulf Publishing, Houston, TX,
1997.
[3] S. Adhikari, S. Fernando, Hydrogen membrane separation techniques, Ind. Eng.
Chem. Res. 45 (2006) 875.
[4] S. Peramanu, B.G. Cox, B.B. Pruden, Economics of hydrogen recovery processes for
the purification of hydroprocessor purge and off-gases, Int. J. Hydrogen Energy 24
(1999) 405.
[5] D.R. Paul, Y.P. Yampol’skii (Eds.), Polymeric gas separation membranes, CRC
Press, Boca Raton, 1994.
[6] S.A. Stern, Polymers for gas separation: the next decade, J. Membr. Sci. 94 (1994) 1.
[7] R.G. Gardner, R.A. Crane, J.F. Hannan, Hollow fiber permeator for separating gases,
Chem. Eng. Prog. 73 (1977) 76.
174
[8] B. Ernst, S. Haag, M. Burgard, Permeselectivity of a nickle/ceramic composite
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178
CHAPTER FIVE
CARBON MEMBRANES FROM BLENDS OF PBI AND POLYIMIDES FOR
N 2 /CH 4 AND CO 2 /CH 4 SEPARATION AND HYDROGEN PURIFICATION
5.1 INTRODUCTION
The inevitability and prominent importance of separation technology in various
sectors of energy and chemical industries is well recognized. Particularly, a significant
growth can be realized in development of technologies related to the separation of
gaseous species. This is, perhaps, driven largely by the great demand for purified natural
gas and other gases for industrial and pharmaceutical applications. For instance, by
considering natural gas sector alone, it is estimated that about 41% of the proven gas
reservoirs in the United States are sub-quality thus require upgrading by removal of
excessive CO 2 , N 2 and H 2 S and other impurities in order to meet the requirements for
pipeline transmission or wellhead processing [1].
Despite the presence of numerous established technologies (e.g., liquid
absorption, pressure swing adsorption, etc.) amenable to gas separations, it can be
realized that in recent years, extensive research studies has been devoted to devising new
techniques with potentials to bring cost-effectives and less complexities in process
179
operation and control. The progressive emergence of membranes that enjoy distinctive
inherent features such as high energy efficiency, ease of scale-up and small footprint has
drawn remarkable perspectives for this technology to become a viable choice for wide
variety of gas separation applications. According to the cited records, gas separation
membrane technology has turned to a $150 million/year business (in 2002) and yet
significant growth is anticipated for it in the near future [2]. Therefore, further
achievements toward maturization of membrane technology require extensive scientific
research and R&D breakthroughs to overcome the challenges.
Besides commercially available polymeric membranes which are gaining more
popularity, carbon membranes constitute a novel and attractive class of membranes with
distinctive features and outstanding gas separation performance. The very good chemical
and thermal stability and capability to surpass the permeability-selectivity trade-off are
considered among the prominent characteristics of carbon membranes [3,4]. From the
technical point of view, carbon membranes perhaps can be considered as true elements in
manifestation and realization of the role of morphology in separation performance. This
is based on the fact that the porous structure allows the high permeability (high
productivity) while the molecular sieving network provides the efficient size and shape
discrimination of molecules (high selectivity) [5]. Carbon membranes are basically
formed through the pyrolysis of polymeric precursors. Extensive studies have revealed
that chemical structure of the polymer, microstructure of the precursor and pyrolysis
process parameters are among the key factors determining transport properties of
resultant carbon membranes [5-10]. In other words, all these parameters play a part in
180
achieving the ultimate goal of obtaining a masterfully structured membrane comprised of
uniquely distributed pores with critical dimensions and desired surface properties.
High attentions have also been paid to the prominent effect of the precursor type;
hence various polymeric materials have been investigated for fabrication of high
performance carbon membranes for gas separation [11-16]. Basically, material selection
is inevitably one of the fundamental criteria for preparation of almost any kind of
membranes and particularly for gas separation. Therefore, apart from the fabrication
technology, it is anticipated the candidate material to possess the prerequisite properties
required for performing the designated functionality. Although, the same concept applies
to the carbon membranes but, in most cases, the candidate materials should meet even
more stringent requirements. For instance, good chemical and thermal stability as well as
amenability to retain the macromolecular structures and network integrity during
pyrolysis process are regarded as additional key prerequisites for achieving the desired
properties in carbon membranes. Of the recent developments, Zhang et al [11] studied the
properties and gas separation performance of a novel poly(phthalazinone ether sulfone
ketone)(PPESK)-based carbon membranes for various gas pairs. Based on their
observations, the resultant carbon membranes could exhibit good separation
performances comparable to polyimide-based carbon membranes. In another work, David
et al. [12] selected polyacrylonitrile (PAN) as the precursor to study the influence of
thermo-stabilization process and soak time leading to fabrication of carbon membranes
with enhanced performance for O 2 /N 2 separation.
181
Abundance of publications, especially in recent years, unanimously corroborate
the prominent position of polyimides as adequate precursors for preparation of carbon
membranes [6,9,17-31]. This is believed to be owing to the distinctive properties of
polyimides like rigidity, high melting point and T g while good chemical and thermal
stability. Thus various classes of polyimides including those containing
hexafluoroisopropylidene (6FDA) groups [20-21], P84 [10, 25, 40], pyromellitic
dianhydride (PMDA, Kapton) [9, 23, 27, 32-34], 1,4,5,8-Naphthalene tetracarboxylic
dianhydride (NTDA)- [35], benzophenone tetracarboxylic dianhydride (BTDA)-
[18,29,36-38] and 2,4,6,-trimethyl-1,3-phenylene diamine, 3,3’,4,4’-
biphenyltetracarboxylic dianhydride (BPDA)-[19,22] based polyimides have undergone
investigations. A comprehensive reference on the carbon membranes derived from the
family of polyimides is tabulated elsewhere [39]. Among all, Matrimid is widely
recognized as it is largely available as a commercial product [18, 29, 37-38, 40]. This is
more highlighted noting the fact that Matrimid have been used as a model polymer for
studying the porosity and its related effects on gas separation properties of carbon
membranes [18]. Jiang et al. employed Matrimid for fabrication of hollow carbon fiber
membranes [40]. Based on this study, although the results of single layer hollow fibers
were not attractive, but the inclusion of Matirmid as an inner layer followed by an outer
PSF-beta mixed matrix layer resulted in significantly enhanced gas separation
performance. In another attempt aiming improvements in gas transport and separation
performance of carbon membranes, Tin et al. [38] applied the chemical modification and
solvent treatment techniques on precursors prepared from Matrimid. The results revealed
182
the effects of swelling caused by solvent and presence of an optimum cross-linking
density.
Vast experiences have revealed the interesting advantages offered by the
involvement of blending technology into the area of polymeric gas separation
membranes. However, there can be found that only few and limited number of studies
have further extended the idea of blending for development of carbon membranes [41-
47]. It should be noted that majority of these reports are published in recent years which
may reflect a positive trend toward this approach. The main objective of this research
study is to explore the advantageous of employing blending technique in enhancing the
gas separation performance of carbon membranes. It is anticipated that blending can be
used as a simple while effective and efficient tool in tailoring the properties of
membranes. The foremost attention was paid in selection of materials amenable to form a
homogeneous matrix and fulfill the expectations. As a result, four high performance
polymers were selected to perform a comprehensive investigation. The aim was further
enriched by systematic investigation and involvement of other parameters including
pyrolysis temperature, blend composition and chemical modification. Membranes were
eventually analyzed with respect to their gas separation performance. Results revealed
that interesting gas permeability and permselectivity could be achieved in carbon
membranes engineered by blending and selection of a proper set of parameters. It is
believed that the knowledge obtained in this study not only provides a useful guideline
for further development of membranes with unique structures but also introduces a new
class of high performance membranes with attractive potentials for various gas
183
separations including nitrogen removal from natural gas streams which has been
suffering from technological limitations among membrane applications.
5.2 EXPERIMENTAL
5.2.1 Materials
Four types of materials were selected and examined in this study.
Polybenzimidazole (PBI, poly [2,2’-(1,3-phenylene)-5,5’-bibenzimidazole], a high
performance polymer with a high glass transition temperature, outstanding thermal
stability and chemical resistance was used as the main polymer. PBI was supplied by
Aldrich Chemical Company Inc. (Milwaukee, USA). Three other commercially available
polymers were selected as partners for preparation of blends with PBI. Matrimid® 5218
(poly [3,3'4,4'-benzophenone tetracarboxylic dianhydride and 5(6)-amino-1-(4'-
aminophenyl-1,3-trimethylindane)], BTDA-DAPI) was purchased from Vantico
(Luxemburg). Torlon® 4000T, a polyamide-imide, was supplied by Solvay Advanced
Polymers and P84 (copolyimide of 3,3’4,4’-benzophenone tetracarboxylic dianhydride
and 80% methylphenylenediamine + 20% methylenediamine) was provided by Lenzing.
The chemical structure of these polymers is shown in Figure 5.1. P-xylene diamine
(PXDA) was supplied by Merck (Germany) and used as the cross-linking agent. N-
Methyl-2-pyrolidone (NMP) and methanol were also procured from Merck and used as
solvents for polymers and the cross-linking agent, respectively.
184
(a)
(b)
(c)
(d)
Figure 5.1. Chemical structure of (a) Polybenzimidazole (PBI) (b) Matrimid® 5218 (c)
Torlon® 4000T and (d) P84.
5.2.2 Preparation of polymer precursors
Polymeric precursors were prepared as dense flat films in three compositions (i.e.,
25/75, 50/50 and 75/25 wt. %). Additional membranes were prepared purely from
individual polymers of Matrimid, Torlon and P84 as standard samples for comparison.
The total solid concentration in each solution was controlled at 2 wt. % in NMP. The
185
detailed preparation procedures including polymer dissolution, casting steps, and solvent
evaporation profile are reported elsewhere [48].
5.2.3 Chemical modification of membranes
Chemical modification of membranes was carried out through application of
cross-linking agent. For this purpose, blend precursors made of Matrimid and PBI were
immersed in solutions comprised of 10 wt.% p-xylene diamine in methanol for two
distinct periods of 5 and 10 days. At the end of the process, each film was washed with
fresh methanol followed by drying in vacuum oven at 120°C for overnight.
5.2.4 Preparation of carbon molecular sieve membranes
The pyrolysis process was performed in a vacuum furnace manufactured by
Centurion Neytech Qex. Polymeric precursors were carbonized under vacuum (2 mm-
Hg) while sandwiched in between two metallic wire meshes. Three different protocols
schematically illustrated in Figure 5.2. were applied. According to the information
provided in this figure, three temperatures of 600°C, 700°C and 800°C were set as final
pyrolysis temperatures attributed as A, B and C protocols, respectively. The heating rates
were controlled following a ramp function, starting with 15°C/min, with consecutive
lower rates of 4°C/min, 2.5°C/min and finally 0.2°C/min. The dwelling time at final
temperature was 2 hrs in all protocols. At the end of the process, the membranes were
cooled down steadily to room temperature.
186
Dwell for 2 hrs
800°C Protocol C
750°C
550°C
Dwell for 2 hrs

Temperature (oC)
250°C
700°C Protocol B
600°C
500°C
Dwell for 2 hrs

250°C
600°C Protocol A
550°C
400°C
250°C
15 oC/min 4 oC/min 2.5 oC/min 0.2 oC/min 0 oC/min
Pyrolysis progress and temperature increment rate
Figure 5.2. Representation of carbonization protocols used in this study with three
distinct final temperatures; protocol A: 600oC; protocol B: 700oC; protocol C: 800oC.
5.2.5 Characterization techniques
Several techniques were used in this study for the characterization of precursors
and their derivative carbon membranes. Differential scanning calorimetry (DSC) was
employed for the evaluation of glass transition temperature (T g ) of individual polymers
and blended precursors. Two consecutive scans from 50 to 450°C at the heating rate
10°C/min (under nitrogen purging) were performed for each sample on a Mettler Toledo
calorimeter (model DSC822). The mid-point of transition temperatures in the second scan
were reported as T g and for evaluation of the miscibility of fabricated precursors.
187
The trend of changes in weight loss during carbonization was simulated using the
Thermogravimetric Analysis (TGA) technique. The analyses were carried out on a
Shimadzu TG-DTA (DTG-60AH) using N 2 as purging gas at the flow rate of 50 ml.min-
1
. The applied temperature range was from 50 up to 900°C.
The microstructural properties of precursors and carbon membranes were
analyzed on X’Pert PRO-MRD wide-angle X-ray diffractometer (XRD) from
PANalytical. The measurements were carried out using Cu Kα radiation with a
wavelength of λ = 1.54 Å at room temperature. The scan range was from 4 to 70

˚ with a
step increment of 0.02˚ s -1. The average d-spacing was determined based on the Bragg’s
law according to the following formula:
nλ = 2d sin θ (5.1)
the inter-segmental spacing between the polymer chains and θ indicates the diffraction
angle. The d-spacing values are interpreted as the average chain spacing.
The elemental analysis was conducted using X-ray photoelectron spectroscopy
(XPS) for scanning carbon, nitrogen and oxygen atoms. The measurements were
performed on a Kratos AXIS-HSi spectrometer with a built-in charge neutralization
system and dual anode Al/Mg X-ray source operating at 300W (15 kV, 20 mA).
5.2.6 Gas permeability and sorption measurements
188
The gas permeation properties of precursors and carbon membranes were
determined by a constant-volume method according to the procedure described in detail
elsewhere [49]. The pure gas permeability for carbon membranes was measured in a
sequence of He, H 2 , N 2 , CH 4 , CO 2 and O 2 at 35 °C. The gas permeability was
determined from the rate of pressure increase (dp/dt) at steady state using the following
relationship:
273.15 × 1010 Vl  dp 
P=   (5.2)
760 AT (( P0 × 76) / 14.7)  dt 
where P is the gas permeability of a membrane in Barrer (1Barrer = 1×10-10 cm3 (STP)-
operating temperature (K) and the feed gas pressure in the up-stream is given by P 0 in
psia. The H 2 permeability test was conducted at 3.5 atm while the testing pressure for
other gases was 10 atm. The ideal selectivity for gas A to gas B was defined as follows:
PA
α A/ B = (5.3)
PB
The sorption properties of carbon membranes were evaluated for N 2 and CH 4
gases using a Cahn D200 microbalance sorption cell. Approximately 60 mg of membrane
was used during each test. The testing temperature was 35°C and sorption equilibriums
data were collected in the pressure range from 0 to 15 atm. The amount of dissolved gas
was calculated after accounting the buoyancy correction factor. The solubility
coefficients were then calculated using the following equation:
189
C
S= (5.4)
p
in which C represents the amount of sorption (cm3 (STP) gas)/(cm3 membrane) at the
corresponding pressure p (10 atm). The diffusion coefficients were calculated using
D=P/S, where P and S are the permeability and solubility coefficient, respectively.
5.3.1. The physical and transport properties of polymers and blend precursors
PBI is a high performance polymer which its properties well meet the
requirements for preparation of carbon membranes. Nonetheless, seemingly the major
impediment which has hampered the wide application of PBI is the limited solubility in
common solvents. In addition, it has been observed that extraordinary brittleness often
encumbers the formation of free-standing films from PBI solutions [50]. The latter is
ascribed mainly to the presence of excessive aromatic rings in the repeating units of the
polymer as shown in Fig. 1. The good compatibility of PBI with other polymers
(especially polyimides) [51-53] originated the idea of employing blending technique to
exploit the advanced properties of PBI in preparation and development of desirable
carbon molecular sieve membranes. In this regard, the interesting capabilities of PBI to
withstand the elevated temperatures and also its stability and endurance toward adverse
environments are expected to be advantageous [54-55]. On the other hand, Matrimid,
Torlon and P84, with well examined and proven excellent properties for membrane
applications were selected as counterpart for PBI. The chemical structure of these
polymers is shown in Figure 5.1.
190
Conceptually, in contrast to the single phased systems, development of carbon
molecular sieve membranes from polymer blends requires a delicate approach and in
most of the cases degree of miscibility is regarded as the key governing factor [56]. In
addition, in such blend systems special attention has to be paid to the phase morphology
which is highly vulnerable to endothermic conditions due to the presence of different
coefficients of thermal expansions especially at temperatures near and above the T g . In
this study, transparency of the films and glass transition temperature (T g ) were used as
criteria to examine the miscibility of polymeric precursors. Table 5.1. provides the results
of Tg measurements for individual polymers as well as blend precursors. The miscibility
on the molecular level could be confirmed as all blend precursors exhibited a single
composition-dependent glass transition temperature falling in the range between the
values obtained for blend constituents. Moreover, the films were completely transparent
and no sign of phase separation could be observed throughout the entire films; further
Table 5.1. The glass transition temperature of polymers and blend precursors measured
by differential scanning calorimetry (DSC).
Polymer Tg (ºC)
PBI 417.5
Matrimid 323.1
Torlon 274.7
P84 315.0
Blends and composition Tg (ºC)
PBI/Matrimid (50/50 wt.%) 375.2
PBI/Torlon (50/50 wt.%) 355.2
PBI/P84 (50/50 wt.%) 390.1
191
corroborating the results of calorimetric experiments. These findings are in good
agreements with earlier research works [51-53]. Fourier Transform Infra-Red (FTIR)
analysis performed as supplementary experiments could also reveal the miscibility of
blend and existence of interaction in the molecular level. Details of FTIR analysis along
with figures can be found elsewhere thus are not repeated here [53,57].
In principle, the basic idea behind the design of polymer blends is to extract
simultaneous benefits from the complementary advantageous properties of each
constituent. This was targeted to employ this idea for advanced gas separation
applications. For this purpose, it is essential that each polymer be sufficiently efficient.
Gas transport properties and separation performance of PBI, Matrimid, Torlon and P84
are provided in Table 2 with the aid of reference [58]. The overall evaluation of data
indicate the lowest gas permeability belong to PBI; most probably due to its peculiar high
chain packing density and rigid structure. The permeability values for the rest of
polymers are relatively higher, following a general trend of P Matrimid > P P84 > P Torlon .
From the separation performance of point of view, the reported PBI data essentially
exhibits the highest selectivity for N 2 /CH 4 and CO 2 /CH 4 . The O 2 /N 2 selectivities
obtained for P84 and Matrimid membrane films were almost comparable and in the range
of 7~8. However, the reported O 2 /N 2 selectivity for PBI is unexpectedly low compared to
the previous proprietary information [59]. On the other hand, P84 exhibits the highest
H 2 /CO 2 selectivity. Therefore, the results indicate that all these polymers essentially
possess reasonably high separation performance; implying tactful selection of materials
to meet the specified requirements.
192
Table 5.2. Gas permeability and ideal selectivity of individual polymers used in this study. a,b
Membrane material Permeability (Barrer) Ideal Selectivity
He H2 O2 N2 CH4 CO2 H2/N2 N2/CH4 CO2/ CH4 O2/N2 H2/ CO2

PBIc 1.05 0.60 0.015 0.0048 0.0018 0.16 125.1 2.66 88.88 3.125 3.75
Matrimid 26.06 27.16 2.00 0.280 0.210 7.00 97.0 1.33 33.33 7.14 3.88
Torlon 5.53 4.44 0.212 0.037 0.030 0.83 120.0 1.23 27.80 5.73 5.32
P84 11.29 9.09 0.402 0.050 0.028 1.37 181.8 1.78 48.93 8.04 6.63
a1 Barrer = 1*10-10 cm3(STP) cm/cm2 s cm Hg
b Testingtemperature: 35oC
c Data obtained from reference [58] with testing temperature : 35oC
193
5.3.2. The effect of pyrolysis protocol on gas separation performance of carbon
membranes
The pyrolysis and its associated parameters as the key processing step for
fabrication of carbon membranes have been the subject of numerous studies. Through
which remarkable effects of heating protocol, final carbonization temperature and its
duration on the morphology of resultant carbon membranes have been appreciated [7, 19,
36]. Essentially it has been found that a typical final temperature for pyrolysis may fall
within the range of 500°C to 1000°C, depending on the type of precursors. The findings
also unanimously suggest that higher temperature and vacuum conditions may yield
carbon membranes with enhanced selectivity but typically at the expense of permeability
for gas separation applications [4,9,41,60]. However, one should also consider the
presence of an optimum temperature at which a molecular sieving microstructure with
balanced separation performance could be produced [19]. In this respect, the optimum
temperature is speculated to be largely dependent on the properties of the precursor and
pyrolysis condition. Thus, in the light of its importance, attention was paid to the
identification of optimum carbonization temperature. In order to avoid unnecessary
complexities, other parameters involved in the process like heating rate, residence time
and atmosphere were adjusted based on our prior experiences and remained identical for
the protocols. Blend precursors from PBI/Matrimid (50/50 wt. %) were selected as the
model samples. The effect of carbonization temperature on gas permeation properties of
resultant carbon molecular sieve membranes are presented in Table 3. From the results, it
could be found that a higher pyrolysis temperature produced carbon membranes with a
lower permeability; the lowest belonging to the membrane carbonized at 800ºC.
194
Table 5.3. The effect of pyrolysis temperature on gas permeability and selectivity of carbon membranes made of PBI/Matrimid
blend precursors. a,b
Precursor components Permeability (Barrer) Ideal Selectivity

& pyrolysis temperature

PBI/Matrimid
459.5 1337 113.2 15.71 5.84 305.5 85.10 2.69 52.31 7.2 4.37
(50/50 wt.%) @ 600oC
PBI/Matrimid
296.6 940.3 54.2 6.3 1.4 169.6 149.25 4.5 121.14 8.6 5.54
(50/50 wt.%) @ 700oC
PBI/Matrimid
112.12 324.0 10.96 1.26 0.278 36.6 257.1 4.53 131.65 8.7 8.85
(50/50 wt.%) @ 800oC
a 1 Barrer = 1*10-10 cm3(STP) cm/cm2 s cm Hg
b Testing temperature: 35oC
195
On the other hand, the increment in pyrolysis temperature was accompanied by
the enhancements in ideal gas pair selectivity. The effect was particularly more tangible
for particular gas pairs like H 2 /N 2 , CO 2 /CH 4 and H 2 /CO 2 which are of relatively larger
difference in kinetic diameter and the values reached up to about 257, 131 and 8.85,
respectively. This may imply the dominant contribution of size discriminative molecular
sieving rather than other mechanisms usually involved in transport of gas molecules in
carbon membranes. This can be interpreted as reduction in pore size, formation of tighter
and more compact structure, limiting in population of larger pores or sharper pore size
distribution upon rising the pyrolysis temperatures. There also have been some thoughts
that pyrolysis temperature may affect the transport properties of membranes through
changes in structural morphology, pyrolysis kinetics of polymer and pyrolysis kinetics of
degraded byproducts [7]. However, experiences have shown that the determination of the
exact contribution of each component is challenging or requires a tedious task.
Elemental analyses of precursors and carbon membranes prepared at various
temperatures could provide further insights over the issue. The results for PBI/Matrimid
blend systems, as shown in Figure 5.3., suggest that the precursor itself contains the
lowest carbon content (83%) but the highest oxygen content (12%). However, the carbon
content starts to increase upon pyrolysis and application of higher temperatures results in
membranes with higher carbon content. As a result, the carbon content of membrane
pyrolyzed at 800ºC could be reached up to about 94%. The observed trend which is
similar to other reports [19] can confirm the progressive evolution of a more graphite-like
structure at relatively higher temperatures. It is also worthwhile to note that a constant
196
depletion occurs in concentration of nitrogen elements upon the increasing the pyrolysis
temperature. The variation in oxygen content was impalpable, similarly observed by
others, probably due to the surface sorption phenomena [20]. The foregoing analysis may
also provide useful information on the elemental evolutions in carbonization process. It
could be seen that oxygen release is stabilized at temperatures about 600°C while the
major progress during the rest of process is on the evolution of other atoms like nitrogen.
A similar trend has been reported by others [61].
40 96
94
35
92
Elemental content (O & N)(%)
Elemental content (C)(%)

30
90
25
88
20
Oxygen
86
Nitrogen
Carbon 84
15
82
10
80
5
78
0 76
precursor 600 700 800
Carbonization Temperature (oC)
Figure 5.3. The elemental analyses of the polymeric precursor and derived carbon
membranes from PBI/Matrimid (50/50 wt. %) at various temperatures. (♦ : Carbon, ■ :
Oxygen, ▲ : Nitrogen)
197
Further structural characterization on carbon membranes was performed by
obtaining XRD spectra as a function of pyrolysis temperature. As shown in Figure 5.4.,
the XRD pattern for membrane carbonized at 600ºC is a merger of two amorphous peaks
appeared at 22.7° and 25.4°. However the increment of the final pyrolysis temperature
turns the peaks toward a single but intensified peak which is shifted slightly toward the
smaller pore sizes; indicating a decrement in average d-spacing. According to the fact
that the d-spacing for carbon membranes is a measure of interlayer distances, one can
infer the formation of more compact structures with higher packing density. In addition,
intensification of another peak located at 2θ=45.1° may be corresponded to the evolution
of more ordered microstructure with efficiently packed graphite layers upon increment of
0.9
0.8 (a) PBI/Matrimid (50/50 wt.%)@800C

(b) PBI/Matrimid (50/50 wt.%)@700C
0.7 (c) PBI/Matrimid (50/50 wt.%)@600C
0.6
Intensity
0.5 2.00 Å
0.4
(a)
0.3
(b)
0.2 3.47 Å
(c)
3.80 Å
0.1
0
10 20 30 40 50 60 70
2 Theta (degree)
Figure 5.4. The effect of variations in pyrolysis temperature on microstructure of
PBI/Matrimid (50/50 wt.%) blend carbon membranes evaluated by X-ray diffraction
analysis.
198
final pyrolysis temperatures [36]. This is of great significance as basically blend systems
are inclined to phase separation phenomena at temperatures close to glass transition
temperatures. This propensity could be more pronounced as the membranes undergo
carbonization which is well above the T g . This can be an indication of the robustness of
blended carbon membranes developed during the entire process. Therefore, the results of
the experiments could identify 800°C as the best pyrolysis temperature which was used
for preparation of carbon membranes throughout the rest of this study.
5.3.3. The effect of temperature protocol on evolution of carbon molecular sieve
membranes
It is well-known that the pyrolysis process is consisting of changes in membrane
morphology in conjunction with the evolution of some elemental components. Some
aspects of this issue were discussed in the previous section. Therefore, it should be
expected that tracking the composition of membrane elements in the course of the
process to provide useful information and insights about the progress of carbonization at
any corresponding stage. In this respect, thermogravimetric analysis (TGA) is the most
widely used and recommended technique. In fact, TGA has been identified as a suitable
means amenable to simulation of the carbonization process [7,9, 60-61]. According to
various reports, TGA has been effectively employed for determination of the temperature
increment protocol during the evolution of carbon membranes. According to the typical
practice the test is being conducted at a certain temperature rate (e.g., 10°C/min) under
nitrogen atmosphere. However, one should note that pyrolysis process is typically carried
out following different ramp functions and under vacuum condition. Therefore, there
199
exists a subtle discrepancy between two procedures and this originated the idea that
perhaps application of TGA with constant protocol may not be a true indicative of an
actual pyrolysis process. This led us to examine the validity of the approach by applying
the real pyrolysis protocols in TGA and evaluate the outcomes. Figure 5.5. shows the
results for PBI/Matrimid (50/50 wt. %) samples using two protocols; one with constant
ramp (10°C/min) (hereinafter: protocol D) and another one with specified ramp function
(i.e., protocol C, also shown in Figure 5.2.). It is interesting to observe distinctive
behaviors particularly with inception from about 350°C and onwards. While the sample
with protocol D exhibits a typical thermogram profile, a comparison reveals that the
100
90
Weight (%)
80
(a)
(b)
70
60 — (a) Protocol C
— (b) Protocol D (10oC/min)
50
0 100 200 300 400 500 600 700 800
Temperature (oC)
Figure 5.5. The results of the thermogravimetric analysis carried out on blend precursor
PBI/Matrimid (50/50 wt. %) applying different temperature protocols. (a) Protocol C (b)
Protocol D (10oC/min)
200
sample degradation in protocol C starts at relatively a lower temperature followed by a
similar weight loss profile. As a result, this stage of degradation is obviously more
extended for protocol C. The stabilization profile then resembles for both conditions till
to about 750°C where a divergence appears in protocol C. The observed features
essentially reflect the effects caused due to the changes in temperature increment rate of
protocol C. Hence, the results can verily highlight the importance of adopting conditions
consistent with the real case pyrolysis in order to avoid any probable mistake in
interpretation of the pyrolysis process.
5.3.4. The effect of blend component on gas separation performance of precursors and
derived carbon membranes
Enough emphasis was given, in the previous sections, to the conspicuous roles of
material selection in obtaining membranes with desired properties. Attempt in this study
was to exploit the synergistic properties of high performance materials through physical
blending. Table 5.4. provides the measured gas permeation values for precursors
fabricated from blending PBI and three other polymers; namely Matrimid, Torlon and
P84. The results show that permeability of blend precursors essentially fall in the range
between that of corresponding values obtained for individual polymers (Table 5.2.). It is
also evident that incorporation of PBI macromolecules which are consisting of rigid
aromatic chains brings a diminishing effect on permeation properties of membranes. The
influences caused by blending are different for each pair which possibly reflects the
nature and intensity of the interactions involved. The greatest effect could be observed for
PBI/Matrimid blend in which the permeability was dropped in average to about the half
201
Table 5.4. The effect of blend components on gas permeability and ideal selectivity of polymeric precursors. a,b

& composition
PBI/Matrimid
13.55 13.06 0.58 0.072 0.045 2.16 181.38 1.6 48.00 8.05 6.05
(50/50 wt.%)
PBI/Torlon
4.38 3.75 0.151 0.023 0.021 0.615 163.04 1.1 29.28 6.57 6.10
(50/50 wt.%)
PBI/P84
7.52 6.88 0.389 0.067 0.056 1.60 102.68 1.2 28.61 5.81 4.30
(50/50 wt.%)
202
of original value for Matrimid. This is possibly owing to the strong interaction between
the functional groups. In comparison, a less reduction in permeability was observed for
other blends. On the other hand, it seems that no definite trend could be established for
variations in permselectivities.
Taking into the account the eminent role of phase morphology in tailoring the
physical properties and subsequently transport properties of polymeric blend membranes,
the results can be regarded as further indication of successful miscibility in molecular
level. In other words, another implication of the permeation tests is to assure the
successful progress of critical preliminary steps before proceeding to the carbonization
stage. Therefore, the above results could ensure the fulfillment of the requirements. The
gas permeability and selectivity of carbon molecular sieve membranes derived from
blend precursors are presented in Table 5.5. As could be expected from the nature of
carbon membranes, the resultant membranes exhibit much larger permeability compared
to their corresponding precursors. Also, interesting to note is that gas permeability of
carbon membranes follows an opposite trend compared to that observed in the precursors.
For instance, polymeric membrane from PBI/Torlon (50/50 wt.%) offering the lowest gas
permeability among the precursors was found to exhibit that of the largest upon
carbonization. On the other hand, permselectivities in almost all cases were raised to
some extent, depending on the type of gas pair. Table 5.6. provides the gas permeability
and selectivity of carbon membranes fabricated from each individual polymer for
comparison. Essentially, it could be observed that compared to other blended carbon
membranes, the one derived from PBI/Matrimid (50/50 wt.%) possesses the largest
203
Table 5.5. The effect of blend components on gas permeability and ideal selectivity of carbon membranes. a,b,c

& composition
PBI/Matrimid
112.12 324.0 10.96 1.26 0.278 36.6 257.1 4.53 131.65 8.7 8.85
(50/50 wt.%)
PBI/Torlon
350.02 970.3 56.61 6.24 2.83 279 155.5 2.20 98.58 9.07 3.47
(50/50 wt.%)
PBI/P84
222.25 355.2 13.21 1.83 0.568 60.54 194.1 3.22 106.58 7.21 5.87
(50/50 wt.%)
c Pyrolysis temperature: 800ºC
Table 5.6. Gas permeability and ideal selectivity of carbon membranes derived from individual polymers. a,b,c

Matrimid 398.1 1279 79.37 12.92 4.486 300.9 98.99 2.88 67.08 6.14 4.25
Torlon 136.1 390.1 8.39 3.084 2.351 43.06 126.49 1.31 18.31 2.72 9.06
P84 585.1 1151 37.43 4.90 2.147 144.2 234.89 2.28 67.16 7.63 7.98
a1 Barrer = 1*10-10 cm3(STP) cm/cm2 s cm Hg
b Testingtemperature: 35oC
204
selectivity for majority of gas pairs including H 2 /N 2 , N 2 /CH 4 , CO 2 /CH 4 and H 2 /CO 2 .
However, the O 2 /N 2 selectivity for this membrane is comparable and slightly lower to
that of PBI/Torlon (50/50 wt.%). This trend can be ascribed primarily to the difference in
microstructural properties. According to the XRD patterns shown in Figure 5.6., the
peaks are appeared at almost the same loci (2θ=25.58 & 45.16) indicating apparently no
difference in the average d-spacings (3.47 and 2.00 Å) between the membranes.
However, the higher peak intensities suggest the increase in regularity and packing order
which can effectively explain the observed trend in permeation results. This reveals that
the precursor morphology can play an important contribution in bringing about such final
properties.
0.9
(a) PBI/Matrimid (50/50 wt.%)
0.8
(b) PBI/P84 (50/50 wt.%)
0.7 (c) PBI/Torlon (50/50 wt.%)
0.6
Intensity
0.5
2.00 Å
0.4
(a)
0.3
(b)
0.2 3.47 Å
(c)
0.1
0
10 20 30 40 50 60 70
2 Theta (degree)
Figure 5.6. The effect of blend component on structural characteristics of blend carbon
membranes evaluated by XRD analysis. (Pyrolysis temperature: 800oC)
205
5.3.5. The effect of blend composition on transport properties of carbon membranes
It is widely shown that composition plays an important role in governing the
physical and chemical properties of blend systems. Our prior experiences have also
confirmed that the transport properties could largely be influenced by variation in blend
composition [48]. The subject was further extended to carbon membranes, as part of this
study, to explore whether and how the variation in composition could affect the
membrane microstructure, morphology and subsequently the gas transport properties.
The effect was investigated on blends made of PBI and Matrimid, primarily due to their
superior performance compared to the other systems. Table 5.7. provides the gas
permeability and selectivity evaluated for three different compositions. One can clearly
witness a large difference in permeability values of the samples; essentially the larger
PBI content has brought about a lower permeability. It can be noticed that the gas
permeability has increased up to 10 to 27 folds upon upgrading the Matrimid content
from 25% to 50% and 75%, respectively. The results also show that, compared to other
samples, the one with highest PBI content can be considered as a more viable candidate
for H 2 /CO 2 separation exhibiting the permselectivity of about 9.2. Achieving such good
performance can possibly be due to the contribution of rigid PBI chains with high
packing density that can have large effects on the chain configurations within the
membrane context and also pore formation during the carbonization process. This might
be in conjunction to the fact that compared to Matrimid, less non-carbon elements are
present in the repeating unit of PBI which can assist in retaining the membrane’s original
stability during carbonization process. As a result, formation of a fine porous structure in
carbon membranes containing higher PBI portions are expected to be responsible for
206
Table 5.7. The effect of blend composition on gas permeability and selectivity of resultant carbon membranes. a,b,c

& composition
PBI/Matrimid
194.10 660.2 30.39 3.78 0.473 96.47 174.6 7.99 203.95 8.04 6.84
(25/75 wt.%)
PBI/Matrimid
112.12 324.0 10.96 1.26 0.278 36.60 257.1 4.53 131.65 8.70 8.85
(50/50 wt.%)
PBI/Matrimid
62.83 148.4 4.22 0.49 0.170 16.13 302.8 2.88 94.88 8.61 9.20
(75/25 wt.%)
207
improved discrimination between H 2 (2.89Å) and CO 2 (3.3Å) molecules. The enhanced
separation performance of PBI/Matrimid carbon membranes for H 2 /CO 2 is depicted in
Fig. 5.7. demonstrating that developed membranes are positioned above the trade-off
line.
100
11
10
9
H2/CO2 ideal selectivity
8 7
10 6
5
4
1 PBIa 1 3 2
2 Matrimid
3 PBI/Matrimid (25/75 wt.%)
1 5 PBI/Matrimid (75/25 wt.%)
6 PBI/Matrimid (25/75 wt.%) carbonized @ 800ºC
9 PBI/Matrimid (25/75 wt.%)+5 days p-xylene diamine X-linking carbonized @ 800ºC
10PBI/Matrimid (50/50 wt.%)+5 days p-xylene diamine X-linking carbonized @ 800ºC
0.1
0.1 1 10 100 1000
H2 permeability (Barrers)
Fig. 5.7. Performance of PBI/Matrimid blend precursors with various compositions and
their corresponding carbon membranes for H 2 /CO 2 separation with respect to trade-off
line. (aData from Ref. [58])
On the other hand, the results obtained by variation in composition indicate that
carbon membranes can also offer high separation performance for gases in the range of
larger molecular size. This would particularly be very attractive for separation of N 2 and
CO 2 from CH 4 . According to the data in Table 5.7, gradual reduction in PBI content of
208
precursors could provide carbon membrane with enhanced N 2 /CH 4 and CO 2 /CH 4
selectivity. Surprisingly, the enhancement in separation performance was very eminent
for N 2 /CH 4 and a selectivity of about 8 was obtained in carbon membrane derived from
PBI/Matrimid (25/75 wt.%). To our best knowledge, this is the highest ever reported
selectivity for this gas pair. Data in Figure 5.8. can clearly demonstrate the high impact of
achieving such high selectivity with enhanced permeability (P N2 =3.78 Barrer).
100
N2/CH4 ideal selectivity
10 6
7
8
1
5
1 PBIa 4
1 3 2
2 Matrimid
6 PBI/Matrimid (25/75 wt.%) carbonized @ 800oC
0.1
0.001 0.01 0.1 1 10 100 1000
N2 permeability (Barrers)
and their corresponding carbon membranes for N 2 /CH 4 separation with respect to trade-
off line. (aData from Ref [58]) (Trade-off line was drawn based on data points retrieved
from Ref. [62])
209
In this respect, study by Cecopieri-Gómeza et al. [62] can also shed lights on the
limitations of polymeric membranes and particularly polyimides for separation of
N 2 /CH 4 and similar gas pairs. Data in Figure 5.9 readily demonstrates the enhanced
CO 2 /CH 4 performance of carbon membranes compared to the trade-off line for this gas
pair.
1000
6
7
CO2/CH4 ideal selectivity
8
100
1
1 PBIa 5
10 2 Matrimid 4
4 PBI/Matrimid (50/50 wt.%) 3
1
0.01 0.1 1 10 100 1000
CO2 permeability (Barrers)
and their corresponding carbon membranes for CO 2 /CH 4 separation with respect to trade-
off line. (aData from Ref. [58])
The interesting properties of developed carbon membranes for the separation of
N 2 and CO 2 from CH 4 can possibly be attributed to the effective contribution of
diffusivity selectivity. This hypothesis was drawn from the careful scrutiny of the
210
spectacular transport properties of carbon membranes. According to an earlier study by
Singh et al. [63], the enhanced selectivity in carbon membranes is found to be due to the
prominent effect of diffusivity selectivity than the solubility selectivity. It should be
noted that the situation is however, different in polymeric membranes in which the effects
of both solubility and diffusivity selectivities are considerable. In fact, the concept of
diffusivity selectivity in carbon membranes has been extended by applying the transition
state theory and taking into account the physical properties of gas molecules. The results
indicated that among the two components of diffusivity selectivity, the effect entropic
selectivity was more significant compared to that of energetic selectivity. This was
attributed to the special provision of preferential transport in finely tuned pathways
within the graphite micro-crystals of carbon membranes [63].
The results obtained from the sorption tests further verified the significant role of
diffusivity selectivity in enhanced separation performance of derived carbon membranes.
The experiments were carried out on carbon membrane derived from PBI/Matrimid
(25/75 wt.%) using N 2 and CH 4 gases. Figure 5.10. presents the amount of sorption at
equilibrium against the testing pressure. It can be seen that the membrane has essentially
exhibited a greater sorption affinity toward CH 4 compared to N 2 over the studied
pressure range. The difference in sorption directly translates it effect into solubility
coefficients and as a result, membrane exhibited a solubility selectivity equivalent to
α S,N2/S,CH4 = 0.66 (S N2 =4.9 and S CH4 =7.4 (cm3(STP)/(cm3.atm)). Besides the effect of
membrane properties, the favorable solubility of methane is partially due to the larger
condensability of CH 4 molecules. (T b,CH4 =112K; T b,N2 =77K). The above results are in
211
good agreement with our hypothesis on the dominant effect of diffusivity selectivity (i.e.,
α D,N2/D,CH4 = 12.1) in achieving the enhanced separation performance of membranes for
N 2 /CH 4 . Possessing such enhanced diffusivity selectivity may indicate the formation of
finely tuned pores in the microstructure of carbon membranes that can constrict or retard
the transport of large molecules like CH 4 . The molecular passage in such network is
possibly permitted only to those molecules which have given up certain degrees of
translational/rotational /vibrational freedom or are aligned in a favorable direction with
respect to the pore geometry.

C [cm 3(STP)/cm3(membrane)]
CH4
N2
Figure 5.10. Plots of N 2 and CH 4 sorption isotherms for the carbon membrane derived
from the blend precursor composed of PBI/Matrimid (25/75 wt.%). (Pyrolysis
temperature: 800oC)
212
The results of XRD analysis on these carbon membranes (Figure 5.11.) can also
provide further support to our hypothesis. Although almost no tangible shift was occurred
in the position of indicative peaks, but evolution of more ordered structural morphologies
could be witnessed by the increments in intensity of the peaks upon increase in Matrimid
content. Therefore, developed carbon molecular sieve membranes from blends of PBI
and Matrimid based on the prescribed procedures can be considered as potential
breakthroughs for practical implementation of membranes for nitrogen rejection from
natural gas. This is particularly more interesting for real case application as favorable
permeation of nitrogen than methane can bring substantial savings in costly and energy
intensive recompression of natural gas.
0.9 (a) PBI/Matrimid (25/75 wt.%)

(b) PBI/Matrimid (50/50 wt.%)
0.8
(c) PBI/Matrimid (75/25 wt.%)
0.7
0.6
Intensity
0.5
0.4
(a)
0.3 (b)
(c)
0.2
0.1
0
10 20 30 40 50 60 70
2 Theta (degree)
PBI/Matrimid blend carbon membranes evaluated by XRD analysis. (Pyrolysis
temperature: 800oC)
213
Figures 5.12 (a), (b) and (c) demonstrate the performance standing of the carbon
membranes for O 2 /N 2 , H 2 /N 2 and H 2 /CH 4 separations.
100
(a)
O2/N2 ideal selectivity
10 8 7 6
5 4
3 2
1 PBIa
1 2 Matrimid
0.1
0.001 0.01 0.1 1 10 100 1000
O2 permeability (Barrers)
1000
(b)
11
10
9
H2/N2 ideal selectivity
8
5 7
4 6
100 1 PBIa 1 3
2 Matrimid 2
10
0.1 1 10 100 1000
214
10000
(c)
H2/CH4 ideal selectivity 9

11 10
1000 7 6
5
1 4 8
3
100 1 PBIa 2
2 Matrimid
10
1
0.01 0.1 1 10 100 1000
and their corresponding carbon membranes with respect to trade-off line for various gas
pairs. (a) O 2 /N 2 (b) H 2 /N 2 (c) H 2 /CH 4 . (aData from Ref. [58])
5.3.6. The effect of chemical modification on properties and gas separation
performance of carbon membranes
Various types of cross-linking methods have attracted attentions as viable means
for tailoring the properties of membranes, and particularly to modify the substructure in
micro- and nano-domain levels. This subject was highlighted in an earlier report
describing the various aspects and consequences of applying such chemical modification
on polymeric materials. For instance, an altered morphology and improved gas separation
performance could be achieved in carbon membranes derived from treated precursor [64].
215
However, it can be realized that this attempt has only been practiced on membranes
composed of a single polymeric component. On the other hand, the experiences obtained
from employing similar approach on polymeric blend membrane has revealed that
chemically modified blend membranes could potentially yield an improved separation
performance [48]. Interestingly, it was revealed in the course of that study that each
component in the blend may respond differently to the modifying agents. Specifically, in
membranes prepared from Matrimid/PBI, more favorable results could be achieved by
the modification of Matrimid phase compared to that of PBI.
An idea was originated to further extend the concept and explore the applicability
of the approach to identify the effects of chemical modification prior to carbonization and
its subsequent influences on the properties and performance of resultant carbon
membranes derived from polymeric blend precursors. P-xylene diamine was selected as
the chemical agent for cross-linking due to its high degree of solubility in the medium
(i.e., methanol, a non-solvent for polymers) and high reaction efficiency. The carbon
membranes derived from the cross-linked precursors were tested and the measured gas
permeability and selectivity values are provided in Table 5.8. Comparison of the results
with corresponding unmodified counterparts (Table 5.7.) indicates a significant decline in
permeability values upon modification. Additionally, the selectivity values have also
been affected and two distinct trends could be recognized. Firstly, the permselectivity for
the gas pairs with negligible difference in molecular dimensions (e.g. N 2 /CH 4 , CO 2 /CH 4
and O 2 /N 2 ) are essentially declined, seemingly as a result of tighter structures provided
by the linkages among macromolecules. On the other hand, favorable enhancements were
216
Table 5.8. The effect of application of a 5-day cross-linking modification by p-xylene diamine (PXDA) on the gas transport
properties of blend carbon membranes with various compositions. a,b,c

& composition
PBI/Matrimid
71.16 182.7 2.615 0.392 0.195 11.00 466.1 2.01 56.41 6.67 16.61
(25/75 wt.%)
PBI/Matrimid
34.77 91.0 0.826 0.172 0.104 3.71 529.1 1.65 30.50 4.80 24.52
(50/50 wt.%)
PBI/Matrimid
23.91 63.2 0.357 0.109 0.081 1.89 579.8 1.34 13.23 3.28 33.44
(75/25 wt.%)
217
achieved in selectivity for gas pairs possessing larger differences in dimensions. For
instance, depending on the blend composition, the gas pair selectivity for both H 2 /N 2 and
H 2 /CO 2 has boosted up to the values in the ranges of 466.1~579.1 and 16.61~33.44,
respectively.
These results can be explained by taking into account the specific role and
contributions of the cross-linking agent in the membranes. Based on the simulation
studies [48], it has been verified that cross-linking molecules not only perform as spaces
filling materials within the membrane context but also their presence can bring about
macromolecular reconfiguration and thus influence the membrane morphology through
establishment of covalent bonding between the adjacent macromolecules. This is
expected to improve the structural stability of the membranes to withstand high
temperatures associated with pyrolysis process. This can take effect through among other
contributing mechanisms such as prevention from the sudden structural collapse, tuning
the interstitial spaces between molecules and preserving the structural integrity after
pyrolysis.
By comparing the membranes derived from after cross-linking modification, one
could perhaps anticipate a better separation performance in those containing larger
amount of Matrimid. This is due to the possible higher degree of modification that can
occur during the treatment of precursors. In this regard, the results in Table 8 may look
counterintuitive as upon reduction in Matrimid content, a stepwise improvement in
selectivity could be achieved for gas pairs like H 2 /CO 2 and H 2 /N 2 .
218
The occurrence of such impressive separation performance in carbon membranes
from BPI/Matimrid (75/25 wt.%) compared to the counterparts can be realized by
simultaneous considerations of the cross-linking phenomena and variations in blend
composition. Basically, in one hand, by applying cross-linking modification, all three
membranes are expected to exhibit improved separation performance; the higher
Matrimid content thus should result in the larger improvement. This could be confirmed
by observation of the XRD patterns (Figure 5.13.) which revealed relatively intensified
indicative peaks for these membranes compared to the unmodified ones shown in Figure
5.11.
1.4
(a) X-linked PBI/Matrimid (25/75 wt.%)

1.2
(b) X-linked PBI/Matrimid (50/50 wt.%)
(c) X-linked PBI/Matrimid (75/25 wt.%)
1
0.8
Intensity
0.6
(a)
0.4 (b)
(c)
0.2
0
10 20 30 40 50 60 70
2 Theta (degree)
PBI/Matrimid blend carbon membranes derived from cross-linked precursors. (Pyrolysis
temperature: 800oC)
219
However, on the other hand, the higher Matrimid content translates to the less PBI
content in the blend which according to the discussions in the previous section (Table
5.7.) should result in diminishing effects in separation performance. In other words,
introduction of large Matrimid for achieving high cross-linking efficiency comes at the
expense of benefits offered by inherent properties of PBI phase. Thus, these two factors
compete against each other and alter the membrane performance in opposite directions.
In overall, the results in Table 5.8., imply the more effective and dominant influence of
blend component over chemical modification in controlling the transport and separation
properties of carbon membranes derived from modified precursors. This is in agreement
with the fact that modification through chemical cross-linking is perceived to influence
the limited outermost surfaces of the membranes, whereas the phase composition has a
global effect over the entire membrane structure. As a result, the high separation
performance in BPI/Matimrid (75/25 wt.%) can be ascribed to the enhanced
morphological properties by partial contributions of PBI chains and chemically integrated
Matrimid macromolecules. As illustrated in Figure 5.7. and Figures 5.12. (b) & (C),
carbon membranes derived from chemically-modified precursors stand well above the
trade-off line specifically for H 2 /CO 2 , H 2 /N 2 and H 2 /CH 4 separation.
5.4 CONCLUSIONS
Advanced carbon molecular sieving membranes were fabricated from the blend of
PBI and various polyimides for gas separation applications. Polymeric films fabricated
from blends of Matirmid, P84 and Torlon with PBI were found exhibiting desirable gas
220
transport properties in conjunction with homogenous structure which were believed to fit
the prerequisites for further development and derivation of carbon membranes.
Examination of three carbonization protocols with distinctive final temperatures revealed
achieving a higher efficiency in carbon membranes obtained at elevated temperatures.
This was mainly ascribed to the extent of progress in processing at higher temperatures
which could bring about microstructures with higher carbon concentrations and more
effective pore sizes with desirable distributions. In addition, according to the analyses
carried out in this study, it was found that proper parameter settings might be essential in
order to achieve more realistic insights about the governing pyrolysis process through the
application of TGA.
Derived carbon membranes were found more permeable to gases compared to
their respective precursors. More interestingly, precursors with tighter polymeric
microstructures where found to offer carbon membranes with higher permeability.
Carbon membranes derived from PBI/Matirmid (50/50 wt. %) exhibited more attractive
performance than the other blends. Further investigations on this promising blend system
revealed higher Matirmid content could result in improved permeability while enhanced
selectivity particularly for separation of N 2 and CO 2 from CH 4 . In addition, further
chemical modification of PBI/Matrimid precursors prior to carbonization produced
membranes with enhanced performance for separation of H 2 molecules from N 2 and
CO 2 . Carbon molecular sieve membranes developed in this study surpass various trade-
off lines and are of great potentials for industrial applications.
221
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229
CHAPTER SIX
GAS SEPARATION MEMBRANES DEVELOPED THROUGH INTEGRATION
OF POLYMER BLENDING AND DUAL-LAYER HOLLOW FIBER SPINNING
PROCESS FOR HYDROGEN AND NATURAL GAS ENRICHMENTS
6.1 INTRODUCTION
The higher efficiency and beneficial advantages offered by gas separation
membranes especially in terms of capital investments, operational costs and also energy
requirements have led to the attraction of many attentions toward this process. The
accelerated popularity of using membranes for various applications can largely be
attributed to the growing concerns over global energy resources and the green house
effects caused by CO 2 . This has, however, been in conjunction with the progressing
improvements in the science and technology of membranes and membrane processes.
Some of the most established membranebased gas separation processes include:
separation of hydrogen from its mixtures with nitrogen or hydrocarbons, pre-combustion
and post-combustion capture of CO 2 , nitrogen/oxygen separationand purification from
air, removal of acid gases and water from natural gas streams, organic vapor removal
from air or nitrogen streams, etc.
A chronological review reveals that the current state of gas separation membranes
230
is largely beholden to the notable breakthroughs in both material science and engineering
and also the membrane fabrication technology. Majority of the gas separation
membranes, in early days, were largely fabricated in the form of asymmetric composite
flat or hollow fiber membranes with a selective layer made from a neat material. As a
result, the application of molecular design using blend materials with synergistic
properties was not often reported.
The trend of fabrication of gas separation membranes was revolutionized by the
introduction of phase inversion process in 1960s [1]. The significance of this
technological breakthrough was more realized upon its successful extension to hollow
fibers as the more preferred geometry offering a large surface area per unit volume of
membrane material. The asymmetric structure of the hollow fibers not only could
significantly reduce the resistance against the transport of the species but also could offer
the membrane a good mechanical support.
Further advancement to the membrane fabrication technology was accomplished
by the advent of the co-extrusion technique that could be used for fabrication of dual-
layer hollow fiber membranes. This technological breakthrough was a satisfactory
response, at least at that time, to the high demands for suitable means to exploit the
potential advantages of the newly developed high performance (yet expensive) materials
for membrane separation applications. The new features offered by the dual-layer hollow
fiber membranes, in comparison to the traditional single-layer hollow fibers, created great
potentials for remarkable savings in membrane costs through substituting the functional
231
material with inexpensive alternatives in the support layer. In addition, the dual-layer
architecture provided a greater flexibility for tailoring the membrane morphology and
spinning parameters.
Nonetheless, the fabrication of the dual-layer hollow fibermembranes with
desirable characteristics is still not a trivial task and requires careful considerations from
the physicochemical properties of materials throughout the entire chain of dope
formulation, spinning and phase inversion process. However, the complexity often arises
in the simultaneous co-precipitation of two distinct materials with different formulations.
An ideal dual-layer hollow fiber membrane consisted of an ultrathin dense functional
layer supported by a porous substructure to enable the membrane withstanding high feed
gas pressures. Equally important to the above requirements is that the structure of the
dual-layer hollow fiber membrane must be free from any delamination at the interfacial
region where the two layers meet. It is shown that the delamination problems can often be
minimized or overcome through promoting the integrity of two layers by choosing
compatible materials or using spinnerets with modified designs [2,3].
As highlighted, one of the key benefits of the dual-layer hollow fiber technology
lies in the great opportunities provided for the exploitation of the wide range of high
performance materials for membrane-based separation applications. Liu et al. [4]
developed polyimide/polyethersulfone dual-layer hollow fiber membranes with the
enhanced performance for separation of CO 2 /N 2 and CO 2 /CH 4 . They also found that
chemical modification of the outer layer offered membranes with enhanced stability
232
against CO 2 -induced plasticization. As a result, the desirable performances obtained in
their hollow fibers promoted the viability of using expensive fluoropolyimide for gas
separation applications. In another work by Li et al. [5], dual-layer hollow fibers
membranes were developed by using zeolite-functionalized-PES as the outer layer
supported by the P84 co-polyimide. The fabricated hollow fibers exhibited enhanced
O 2 /N 2 and CO 2 /CH 4 selectivity in the order of around 10–20% compared to the PES
dense films. Jiang et al. [6] investigated the effect of various spinning parameters on
fabrication of defect-free dual-layer hollow fiber membranes using
Matrimid/polyethersulfone (PES) and fiber membranes and evaluated their performance
for O 2 /N 2 and CO 2 /CH 4 separations. They claimed the occurrence of a faster inter-layer
diffusion when the fibers were spun at elevated spinneret temperatures. Another similar
study was carried out by Ding et al. [7] who fabricated hollow fiber membranes using
Matrimid as the outer layer while polysulfone as the inner layer material for O 2 /N 2
separation.
Interestingly, almost all the prior studies on the development of the hollow fiber
membrane were aimed to the separation of H 2 /N 2 , O 2 /N 2 , CO 2 /N 2 , CO 2 /CH 4 but
H 2 /CO 2 . This can possibly be due to the fact that most polymeric membranes show a
relatively poor selectivity for separation of H 2 /CO 2 . The problem arises from the fact that
despite a noticeable difference in the molecular size (H 2 : 2.89Å vs. CO 2 : 3.30 Å) of the
two gases, the solubility of CO 2 in polymers is much higher than that of H 2 .
Consequently, a relatively low permselectivity is achieved owing to the presence of these
competing effects. In addition, CO 2 is a highly condensable gas and its sorption can
233
plasticize the polymeric membrane and increase the interstitial chain spaces. The CO 2 -
induced plasticization typically results in reduced efficiency through deterioration of the
size-exclusion mechanism. As a result, novel membrane materials and fabrication
techniques must be advanced to overcome the obstacles associated with the separation of
H 2 /CO 2 using polymeric membranes. We selected polymer blend technology as a
promising strategy to address these issues. So far, no study could be found on the use of
polymeric blends as the functional material for preparation of dual-layer hollow fiber
membranes consequently no one has reported the use of this type of dual-layer
membranes for H 2 /CO 2 separation. Only limited studies could be found that have used
polymeric blend systems in the form of single-layer hollow fiber membranes [8–10], but
none of them dealt with H 2 /CO 2 separation. This is quite surprising considering the
abundance of numerous studies that have extensively demonstrated the promising
features of polymer blends for a variety of membrane-based gas/liquid separation
applications [11–16]. In addition to material limitation, the other possible reasons for
underutilization of polymerblendsmayinclude the increase in complexity of the dual-layer
hollow fiber spinning process and the difficulty in prediction and control of various
parameters.
To our best knowledge, this is the first study on the application of miscible
polymer blends for fabrication of dual-layer hollow fiber membranes. The main objective
is to develop a novel approach that encompasses the synergistic advantages of the
polymer blending technology and the membrane fabrication process for high performance
gas separation applications. Indeed, this work can be regarded as an extension to our
234
earlier studies [11,12] that reported the development of high performance dense flat
membranes with tunable properties from selected polymer blends. Attempts were made in
this study to unravel the underlying mechanisms and engineering to scale up the flat
dense membranes to dual-layer hollow fiber membranes with desirable features. In this
respect, the effect of various important parameters such as dope flow rate, air-gap
distance and take-up speed on the morphological and gas transport properties of hollow
fiber membranes were investigated. The resultant hollow fiber membranes were analyzed
based on their separation performance for industrially important gas pairs. It is believed
that the knowledge and experience gained throughout this exemplary study can create
greater opportunities for further advancements in the field of membranes and membrane
materials for various gas separation applications.
6.2 EXPERIMENTAL
6.2.1. Materials
A polymer blend composed of Matrimid and poly(benzimidazole) (PBI) was
prepared and used as the outer-layer material for the fabrication of dual-layer hollow
fiber membranes. Matrimid is a commercially available polyimide with attractive
properties and gas separation performance [17-19]. Matrimid® 5218 (poly [3,3’4,4’-
benzophenone tetracarboxylic dianhydride and 5(6)-amino-1-(4’-aminophenyl-1,3-
trimethylindane)], BTDA-DAPI) was purchased from Vantico (Luxemburg) in the form
of powders. PBI (poly [2,2’-(1,3-phenylene)-5,5’-bibenzimidazole]) is also a high
performance polymer with a relatively high glass transition temperature (~418ºC) and
235
outstanding thermal and chemical stabilities. The PBI used in this study was supplied by
Hoechst Celanese Corporation, (NJ,USA) in the solution state with the following
formulation: 25.6 wt.% PBI, 72.4 wt.% DMAc and 2.0 wt.% LiCl.
Polysulfone (PSf) was selected as the inner supporting material. PSf is an
amorphous glassy polymer possessing a reasonably high T g and good stability against
environmental oxidation [20]. Polysulfone (UDEL) was provided by Solvay Advanced
Polymers, Singapore. The chemical structure of PBI, Matrimid and polysulfone is shown
in Figure 6.1.
(a)
(b)
(c)
Figure 6.1. The chemical structure of (a) Polybenzimidazole (PBI) (b) Matrimid® 5218
and (c) UDEL Polysulfone (PSf).
236
Besides polymers, various chemical reagents were also used. N-Methyl-2-
pyrolidone (NMP) and N,N-dimethylacetimide (DMAc) were procured from Merck and
Tedia Chemical Inc., respectively and used for the polymer dissolution. Methanol and
hexane (obtained from Merck) were used during the solvent exchange. p-
Xylylenediamine (PXDA) from Sigma-Aldrich (Germany) was used for chemical cross-
linking modification of the hollow fibers. Methanol was used as the medium for this
process. All chemical reagents were used as received.
6.2.2. Dope formulation and preparation
The outer-layer dope was prepared from a blend comprised of PBI and Matrimid
in 1:1 (weight ratio) composition. According to the literature [21,22], one potentialwayto
eliminate or at least minimize the defects in the dense-selective layer is to properly adjust
the dope formulation. Figure 6.2 demonstrates the trend of changes in viscosity of dope
solutions as a function of polymer concentration. Data were obtained using an ARES
rheometer at the shear rate of 10 s−1. This figure also includes the critical polymer
concentrations (c.p.c.) identified for the individual polymer dopes. Based on these results,
the concentration of 22 wt.% was selected for the preparation of outer-layer dope to
ensure achieving the desired morphology in this functional layer. On the other hand, the
concentration of inner dope was adjusted to 25 wt.% that is sufficiently lower than its
corresponding c.p.c. value (i.e., 29 wt.%). The objective was to minimize the effect of
substructure resistance on the membranes’ performance.
237
Both dope solutions were prepared by adding stipulated amounts of polymers into
the respective solvent followed by rigorous stirring until complete dissolution. Both dope
solutions were degassed in the syringe pumps for at least 24 h prior to spinning.
Figure 6.2. The trend of changes in dope viscosity as a function of polymer concentration
in the respective solvent. (♦ PBI/DMAc, ■ Matrimid/DMAc, ▲ PSf/NMP, ●
PBI:Matrimid (1:1)/DMAc).
6.2.3. Dual-layer hollow fiber spinning process
Dual-layer hollow fiber membranes were fabricated by adopting the dry-jet wet
spinning process. Figure 6.3 depicts the schematic diagrams for the spinning set-up and
the triple-orifice spinneret used in this study. As shown, three high precisions syringe
pumps (ISCO, USA) were employed to co-extrude dope solutions and the bore fluid
through the spinneret at specified flow rates. The solutions were filtered before flowing
238
into the spinneret channels. Table 6.1 provides a summary of the spinning parameters and
conditions. The bore fluid was a mixture of NMP/water (95/5 wt.%) whereas the external
coagulant was merely tap water.
Inner Bore fluid

channel
a b a
Outer
channel
c
2.4 mm
1.4 mm
c c
d
Figure 6.3. Schematics of dual-layer hollow fiber spinning set-up and triple-orifice
spinneret. (a) dope fluid tank and pump; (b) bore fluid tank and pump; (c) filter; (d)
spinneret; (e) coagulation bath and (f) take-up drum.
Table 6.1. The spinning parameters and conditions used in preparation of dual-layer
hollow fiber membranes.
239
Sample ID Outer dope flow Inner dope flow Bore fluid flow Air-gap Take-up speed Fiber collection state
rate (cm3.min-1) rate (cm3.min-1) rate (cm3.min-1) (cm) (cm.min-1)
A 0.20 2.00 1.00 0.0 327 Free fall
B 0.40 2.00 1.00 0.0 327 Free fall
C 0.20 2.00 1.00 1.0 371 Free fall
D 0.20 2.00 1.00 1.0 681 Elongational draw
X 0.20 2.00 1.00 2.0 449 Free fall
Y 0.20 2.00 1.00 3.0 560 Free fall
Outer dope: PBI/Matrimid (1:1), 22 (wt.%) in DMAc;
Inner dope: Polysulfone, 25 (wt.%) in NMP;
Spinning temperature: 25oC
Nascent hollow fibers were collected around a rotating drum after passing through the
coagulation bath. This drum was equipped with a gearing system enabling spinning at
various take-up speeds. As-spun hollow fiber membranes were cut into small pieces and
placed in clean water for about two days. The solvent exchange was carried out by
immersing hollow fibers in methanol for three times, each lasting for about 30 min. This
procedure was repeated using hexane. The fibers were finally dried in ambient
environment.
6.2.4. Silicone rubber coating and chemical modification
Silicone rubber coating was applied, using a solution composed of silicone rubber
(Sylgard-184) in hexane (2 wt.%), to seal the defects and imperfections of the
membranes. Hollow fibers, in the form of modules, were immersed in the solution for 2
min. For chemical modification, hollow fibers were immersed in the solutions of p-
xylylenediamine in methanol (10 wt.%) for stipulated periods of time. The fibers were
then removed and rinsed in fresh methanol in order to strip the unreacted molecules away
from the membrane’s surface.
6.2.5. Membrane characterization and gas permeation tests
240
The morphology of dual-layer hollow fiber membranes was examined using a
JEOL JSM-5600LV scanning electron microscope (SEM) and a JEOL JSM-6700F field
emission SEM. Samples were fractured in liquid nitrogen and then coated with platinum
before observation. The gas permeation properties of the hollow fiber membranes were
analyzed using the variable-pressure constantvolumemethod. This method is described in
details elsewhere [23]. The feed gas was supplied to the shell side of the membrane
module and the permeate side was connected to a vacuumed chamber. All pure gas
permeation tests were carried out at 35oC with the testing pressure of 10 atm for CH 4 and
CO 2 , and 3.5 atm for H 2 . However, during the CO 2 plasticization experiments, the
testing pressure was raised up to about 15 atm. The permeance, P/L, was determined
using the following equation:
𝑃𝑃 𝑄𝑄 𝑄𝑄
= = (6.1)
𝐿𝐿 𝐴𝐴∆𝑃𝑃 𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 ∆𝑝𝑝
where P is the permeability of separating layer (Barrer), L is the thickness of the apparent
dense-selective layer (cm) and Q is the pure gas flux (cm3.s-1). On the right hand side, n
specifies the number of fibers in the testing module, D is the outer diameter of the fiber
(cm), l is the effective length of the fibers (cm), and Δp is the gas pressure difference
across the membrane (cm Hg). The permeance is reported in GPU (1 GPU = 1×106 cm3
(STP)/cm2.s.cm Hg).
The ideal separation factor (α A/B ) was calculated using the following equation:
𝑃𝑃 𝑃𝑃
𝛼𝛼𝐴𝐴⁄𝐵𝐵 = ( )𝐴𝐴 /( )𝐵𝐵 (6.2)
𝐿𝐿 𝐿𝐿
241
6.3.1. Morphological characteristics of dual-layer hollow fiber membranes
Figure 6.4 illustrates the typical morphology of as-spun dual-layer hollow fiber
membranes (sample B). The analysis of SEM images revealed the presence of no major
differences in overall morphology of fabricated hollow fibers, from sample A to sample
Y. However, two distinct morphologies could be seen for the inner and outer layers.
According to Figures 6.4 (d) and (e), the outer layer of the hollow fibers was in the form
of an asymmetric structure; constructed of spongy-like cells surrounded by a thin dense-
selective layer at the outermost edge. No macrovoid could be found in the crosssection
morphology of the outer layer. On the other hand, the inner supporting layer was
considerably larger in thickness with a crosssection occupied by open cell pores and
disrupted by finger-like macrovoids.
d c
X6,000 2 μm X2,500 10 μm
e a b
X10,000 1 μm X500 50 μm
f g
X 25,000 1 μm X 1000 10 μm
242
Figure 6.4. SEM images illustrating various morphological aspects of a typical dual-layer
hollow fiber membrane (sample B): (a) membrane cross-section; (b) membrane sector; (c
and d) inner and outer layers; (e) interface region; (f) outer surface of the outer layer and
(g) inner surface of the inner layer.
The morphological difference between the inner and outer layers can be explained
by taking into account the chemistry of dope components and the coagulation agent.
Table 6.2 provides the solubility parameter values for the polymers, solvents and the
coagulant. According to this table, one could find a negligible difference in the solubility
parameters of NMP and DMAc. On this basis, it was expected for these two solvents to
exhibit a similar interaction with water, especially in terms of diffusion coefficient during
the phase inversion process. On one hand, the data indicate the presence of a relatively
small difference in the solubility parameters of water and the polymer blend compared to
that of water and polysulfone. This results in the slower precipitation rate for the outer
layer. In addition, the characteristics of strong hydrogen bonding provided by PBI and
high viscosity of the outer-layer dope may also inhibit macrovoid formation at the outer
layer [20,27,28]. On the other hand, the greater solubility parameter difference between
water and polysulfone, the low viscosity of the inner dope, and hydrophobicity of
polysulfone were hold responsible for the increased tendency of macrovoid formation in
the structure of inner layer through unbalanced localized stresses, rapid rate of solvent
exchange and the accelerated precipitation rate [20,28–32].
243
Table 6.2. Solubility parameters of the solvents, the coagulation agents and the polymers,
coagulation agents and polymers.*
Component Solubility parameter,

δt (J.cm-3)1/2
NMP 22.9
DMAc 22.7
Water 47.8
PBI 23.3
Matrimid 22.9
Polysulfone 18.0
*Data obtained and calculated using Refs. [24-26].
It could be found from Figure 6.4(e) that as-spun hollow fibers were free from
any delamination at the interface between the inner and outer layers. The delamination-
free structure is usually regarded as one of the key pre-requisites in the fabrication of
dual-layer hollow fiber membranes to ensure consistency in performance of gas
separation membranes throughout the service life. This is due to the fact that delaminated
membranes are highly susceptible to failure and structural collapse at high feed pressures
[2,3,33]. As a result, this subject has attracted special attentions among membrane
specialists. The delamination-free structure of the newly developed dual-layer hollow
fibers can be attributed to (1) good miscibility in molecular level among PBI and
Matrimid polymer chains provided by the strong hydrogen bonding [34–36] and (2) inter-
diffusion of solvents and polymeric chains at the interface driven by the chemical
potential differences and close solubility parameters between two dopes. These unique
combinations can easily eliminate the necessity for using sophisticated spinneret designs
in fabrication of delamination-free hollow fiber membranes [33].
244
According to Figure 6.4(f), the outer skin of the outer layer was essentially dense
with some minor defects scattered over the areas of observation. The dense-selective
layer in asymmetric membranes can often be defective mainly due to the rapid
coalescence of polymermolecules and irregular packing of kinked polymer chains [37].
Number of approaches such as proper dope formulation with favorable rheological
properties [28,37,38], using dual coagulant bath [39], moderate elongation take-up rate
[40], modification of the spinneret design, heat treatment, silicone rubber coating, etc.
have been proposed in order to produce defect-free hollow fibers for gas separation. To
simplify the dope composition and spinning process, silicon rubber coating was selected
to seal the membrane defects before conducting the gas permeation tests in this study.
6.3.2. The effect ofspinning type and air-gap distance on the morphology and gas
transport properties of dual-layer hollow fiber membranes
Figure 6.5 shows the cross-section morphology of dual-layer hollow fiber
membranes spun at various air-gap distances. Higher magnification pictures are provided
below each image. A consistent similarity could be found in the overall morphology of
these hollow fibers.
Hollow fiber membranes were examined for their gas transport properties and
separation performance. Table 6.3 provides the results of gas permeation tests for the
fibers spun at different air-gaps. Data in this table are categorized into two groups of
before and after the application of silicone rubber coating. A relatively poor separation
245
performance was found for the pristine membranes indicating the possible presence of
defective sites in the membranes. Therefore, silicone rubber coating was applied in order
to exclude the effects of defects and imperfections in the analysis of the performance of
the membranes. A significant decline was found in the gas permeance of silicon rubber
coated hollow fibers upon switching from wet to dry-jet spinning. This could possibly be
attributed to the effects of elongational stretch and die swell (will be discussed later).
However, it was noticed that the provision of air-gap resulted in the formation of
amembrane with considerably higher separation performance for H 2 /CO 2 with selectivity
of 8.96 at an air-gap of 1 cm. The selectivity was further improved to about 11.11 for the
246
Figure 6.5. The cross-section morphology of dual-layer hollow fiber membranes spun at different air gap distances.
Sample A (Air gap: 0 cm) Sample C (Air gap: 1 cm) Sample X (Air gap: 2 cm) Sample Y (Air gap: 3 cm)
X80 200 μm
X500 50 μm
247
membrane prepared in 3-cm air-gap. However, spinning with air-gap had a negative
effect on the CO 2 /CH 4 selectivity of membranes.
Table 6.3. The effect of air gap distance on the gas permeance and separation
performance of dual-layer hollow fiber membranes.
Sample ID Air-gap Permeance (GPU) Selectivity (α)

(cm)
H2 CH4 CO2 H2/CO2 CO2/CH4
(±max4.5%) (±max2%) (±max3.2%) (±max3.1%) (±max3.5%)
Before silicone rubber coating
A 0.0 43.22 1.458 7.34 5.89 5.04
C 1.0 30.29 3.542 4.90 6.18 1.38
X 2.0 36.51 2.127 5.48 6.66 2.58
Y 3.0 38.67 1.850 5.65 6.85 3.05
After silicone rubber coating

A 0.0 31.55 0.223 4.37 7.22 19.60
C 1.0 17.84 0.199 1.99 8.96 10.01
X 2.0 26.45 0.273 2.49 10.62 9.12
Y 3.0 29.26 0.328 2.63 11.11 8.03
Spinning Conditions:
Inner dope: Polysulfone 25 (wt.%) in NMP;
Outer dope flow rate: 0.20 cm3.min-1;
Inner dope flow rate: 2.00 cm3.min-1;
Bore fluid flow rate: 1.00 cm3.min-1;
The effect of spinning type (i.e., wet-spun vs. dry-jet) on the microstructural and
transport properties of hollow fiber membranes can be explained by careful examination
of key spinning parameters and their role in phase inversion process. It is known that
flexible polymer coils are fully extended while present in a good solvent but they tend to
contract upon the introduction of a non-solvent [41]. The contraction rate is largely
dependent on the solubility parameter of the system components as well as the amount of
non-solvent. For the fibers spun at zero air-gap distance, the fast and vigorous diffusion
of the water molecules (strong coagulant) results in the sudden contraction of polymer
chains with minimal chance for any orientation or configurations. As a result, the
248
population of the fine pores and free volumes in the membrane’s microstructure are
expected to grow due to the random entanglement of polymer chains [41–44]. This
especially occurs during the solvent exchange process during which the solvent and non-
solvent molecules entrapped among the frozen polymer coils are extracted.
On the other hand, the phase inversion process for the fibers fabricated through
dry-jet wet spinning follows a slightly different pathway [44,45]. In this case, the
properties of hollow fibers are mostly governed by the primary phase inversion in the air-
gap region and also polymer chain orientation. It is documented that moisture-induced
phase separation results in the formation of a relatively dense layer at the outermost skin
of the hollow fibers [44]. The polymer chains in this dense layer are highly oriented due
to the gravity forces induced by the weight of the nascent fiber traveling in the air-gap.
The presence of such a highly oriented and dense skin layer can be regarded as the main
cause for the reduced gas permeance but enhanced gas pair selectivity of the membrane.
In addition, further evolution of the membrane microstructure and the coarsening process
at regions beneath the skin layer is also expected to be affected due to the substantial
reduction in the rate of mass transfer between the solvent and non-solvent (in the
coagulation bath) caused by the skin layer.
It is also interesting to note that a further increase in air-gap distance from 1 cm to
3cm brings about improvement in gas permeance, more noticeably toward H 2 among all.
In terms of separation performance, a larger air-gap further improves the H 2 /CO 2
selectivity of membranes, but at the same time decreases the CO 2 /CH 4 selectivity. One
249
possible reason for the increase in gas permeance is the relatively enlarged interstitial
space of around H 2 size between the polymer chains induced by the weight of the nascent
fiber travelling in the air-gap region. However, seemingly the effect of air-gap distance is
quite limited in provision of more spacious gap between the polymer chains that can
favor passage of all gas molecules. The pronounced improvement in hydrogen permeance
is owing to its considerably smaller kinetic diameter among the others. Consequently, a
higher increase in H 2 permeance compared to that of CO 2 results in an overall increased
H 2 /CO 2 selectivity as a function of air-gap distance.On the other hand, a less enhanced
permeance of CO 2 compared to that of CH 4 results in a less effective discrimination
between CO 2 and CH 4 molecules.
Another possible reason for the effect of air-gap distance can be the increased
intensity of orientation and degree of chain packing, simply due to the larger gravitational
forces induced to the nascent fiber. The occurrence of such phenomena at high air-gaps
provides more resistance to the diffusion of water vapor during the vapor-induced phase
inversion, thus retarding the progress of the precipitation front into the underlying
structure. As a result, fibers spun at the higher air-gaps may possess a thinner dense skin
layer and subsequently promoted gas permeance.
It is noteworthy that the hollow fiber membranes spun at the air-gap distance of 3
cm exhibited the highest separation performance for H 2 /CO 2 (α= 11.11) among all,
exceeding the intrinsic value reported for the dense flat membrane made from the same
outer-layer material (see Table 6.4) [11]. This can possibly be attributed to the combined
250
effects of shear and elongational forces in changing the interaction and micro-
configuration of PBI and Matrimid polymer chains to the state that is much different from
the one dominant in dense flat membranes. In addition, we believe that the presence of
PBI in the polymer blend plays an inevitable role in promoting the overall diffusivity
selectivity of the membranes through (1) the modification of free volumes distribution,
(2) formation of a higher chain packing density, and (3) causing hindrance in segmental
mobility of polymer chains. Occurrence of these effects can be associated to the special
molecular structure of PBI, presence of aromatic rings in the backbone (assistance in
formation of charge transfer complex) and also functional groups capable of forming
strong hydrogen bonding with Matrimid chains. It should be mentioned that despite the
good separation performance obtained in pure gas experiments of membranes, the mixed
gas selectivity (feed gas: H 2 –CO 2 (1:1)) could reach to only about 3.17 possibly owing to
the competitive sorption dominated by CO 2 molecules.
Table 6.4. The intrinsic gas transport properties of the dense flat membrane made from
the polymer blend and respective individual polymers.a
Membrane constituents Permeability (Barrer) Ideal Selectivity
H2 CH4 CO2 H2/ CO2 CO2/ CH4

Matrimid 27.16 0.210 7.00 3.88 33.33
PBI/Matrimid (1:1) 13.06 0.045 2.16 6.05 48.00
PBI 0.6 0.0018 0.16 3.75 88.88
a Data reproduced from Ref. [11]
251
6.3.3. The effect of elongational drawing on the transport properties of dual-layer
hollow fiber membranes
Table 6.5 provides the results of gas permeance and separation factor for
membranes spun at the free-fall state and those spun with elongational drawing, before
and after the application of silicone rubber coating. The results indicate that hollow fiber
spun with elongational drawing exhibits an improved permeance for both hydrogen and
carbon dioxide, but a reduced permeance for CH 4 . This trend of changes consequently
brings about improvements in separation performance of membranes for CO 2 /CH 4 with
enhanced selectivity of 41.81, but reduces the separation performance for H 2 /CO 2 from
8.96 down to 6.79. The membrane was also tested using a mixed gas ofCO 2 –CH 4 (1:1) as
the feed (at 10 atm and ambient temperature) and CO 2 /CH 4 selectivities as high as 26.63
could be achieved.
Table 6.5. The effect of application of elongational drawing on the gas permeance and
separation performance of dual-layer hollow fiber membranes.
Sample ID Fiber collection state Permeance (GPU) Selectivity, α

(±max3.8%) (±max1.5%) (±max3.5%) (±max3.5%) (±max2.9%)
C Free fall 30.29 3.542 4.90 6.18 1.38
D Elongational draw 39.00 0.527 5.76 6.77 10.93

C Free fall 17.84 0.199 1.99 8.96 10.01
D Elongational draw 32.66 0.115 4.81 6.79 41.81
Outer dope flow rate: 0.20 cm3.min-1
Air gap: 1.0 cm;
252
A comparison between the gas permeance values in Tables 6.3 and 6.5 revealed
that the application of elongational drawing is more effective than raising the air-gap
distance in altering the microstructure of the membranes, degree of chain packing and
molecular orientation in the dense skin layer. Therefore, explanations provided in the
previous section can be extended to analyze the effect of elongational drawing on the
performance of the membranes. On this basis, we would like to hypothesize that in
addition to the orientation induced to the polymer chains, the application of elongational
drawing could effectively change the microstructure of the membranes, especially at the
skin layer, to be constructed of tiny pores/free volumes elongated in the direction parallel
to the induced forces. These elongated pores/free volumes are expected to provide a
better pathway for the passage of small and linear molecules (e.g., H 2 and CO 2 ), but to
hinder the passage of molecules possessing polyhedral structures (e.g., CH 4 ).
The above phenomena can clearly demonstrate that spinning at high air-gaps or
with elongational drawing can effectively be employed to fabricate hollow fiber
membranes for specific separation applications. In other words, membrane spun at a high
air-gap distance ismorefavorable for H 2 /CO 2 separation (α H2/CO2 = 11.11), whereas the
one spun with elongational drawing is more suitable for CO 2 /CH 4 separation (α CO2/CH4 =
41.81). It also implies that despite the similarity in the nature of two mechanisms, the
evolution of membrane microstructure during the phase inversion process may follow an
entirely different pathway that is largely governed by the characteristics of the membrane
materials (e.g., rheology, hydro-phobicity/philicity, and coil size), state of
macromolecular orientation, travel time in air-gap region and other important parameters.
253
6.3.4. The effect of outer-layer dope flow rate on the transport properties of dual-layer
It is very obvious that using a low dope flow rate in fabrication of dual-layer
hollow fiber membranes can often be very advantageous especially in terms of the
savings in material costs. However, membranes with an extremely thin functional layer
tend to be more vulnerable to skin defects and other possible imperfections. For instance,
an unbalanced or partial coverage of the outer layer over the supporting layer can easily
destroy the membrane’s functionality. On the other hand, aside from its economical
drawbacks, spinning with excessive outer dope flow rates can result in membranes with
reduced flux and productivity. Therefore, due to its importance, attempts were made in
this study to examine the effect of outer dope flow rate on the gas transport and
separation performance of dual-layer hollow fiber membranes.
Table 6.6 provides the data on the gas permeance and selectivity of hollow fiber
membranes spun at different outer dope flow rates. It was found from the results that an
increase in outer dope flow rate results in considerable reductions in gas permeance of the
membranes. It is also interesting to note amore pronounced drop in membrane’s
permeance toward CH 4 compared to the other gases. For instance, sample B exhibits a
CH 4 permeance of 0.090 GPU which is about 16.2 times lower than the vale for its
counterpart membrane (i.e., sample A). The occurrence of similar phenomena has been
reported in literature in which single-layer hollow fiber membranes spun with higher
dope flow rates exhibited a thicker and denser skin layer with a tighter substructure [46].
254
Table 6.6. The effect of variation in outer dope flow rates on the gas permeance and
separation performance of wet-spun dual-layer hollow fiber membranes.
Sample ID Outer dope flow rate Permeance (GPU) Selectivity, α

(cm3.min-1)
A 0.20 43.22 1.458 7.34 5.89 5.04
B 0.40 22.07 0.090 4.22 5.23 46.84

A 0.20 31.55 0.223 4.37 7.22 19.60
B 0.40 18.89 0.085 2.97 6.36 34.82
The above trends of changes in gas permeance subsequently affect the separation
performance of hollow fiber membranes. In fact, an increase in outer dope flow rate
results in substantial improvements in CO 2 /CH 4 selectivity reaching the values as high as
46.84. However, this is accompanied with a reduction in H 2 /CO 2 separation performance.
The mixed gas selectivity of this membrane for CO 2 /CH 4 is 35.63 when using a mixed
gas of CO 2 –CH 4 (1:1) as the feed at 10 atm and ambient temperature.
The observed trends can possibly be attributed to the larger gas transport
resistance of membranes due to the formation of a thicker dense skin layer. In addition, in
the course of spinning, the polymer dope flows through an annular channel within which
it receives shear stresses through its contacts with the surrounding walls. Due to the fixed
geometry of the channel, a larger dope flow rate translates into a larger axial velocity and
consequently induction of a larger shear stress to polymer chains [47–49]. Therefore, a
dense skin layer is formed possessing a higher degree of molecular orientation and chain
255
packing and evolution of a microstructure that can considerably enhance the distinction
between CO 2 and CH 4 gas molecules. The resultant membrane exhibits promising
performance for natural gas enrichment by having the enhanced CO 2 /CH 4 selectivity as
high as 46.84 without any post treatment.
As anticipated, application of silicone rubber coating on membranes spun with
outer dope flow rate of 0.40 cm3 min-1 resulted in further declines in gas permeance
through sealing the membrane’s defect and also non-selective pores. In addition, silicone
rubber coating was found more effective in improving the H 2 /CO 2 separation of hollow
fiber membranes from about 5.23 up to 6.36.
6.3.5. The analysis of the anti-plasticization behavior of dual-layer hollow fiber
membranes
One of the important factors in evaluation of the long-term performance and
reliability of the gas separation polymeric membranes is their stability against the
plasticization. It is often reported that the plasticization is caused by highly polar gases
such as CO 2 molecules especially when present at relatively high partial pressures. The
incipient point for the plasticization is known as plasticization pressure (P plast ).
Plasticization phenomena are deteriorative to membrane performance through dissolution
of gas molecules into the polymer matrix followed by the disruption of chain packing and
enhancement of their inter-segmental mobility. In this respect, dual-layer hollow fiber
membranes were examined in terms of their anti-plasticization characteristics. This was
achieved through monitoring the trend of changes in the CO 2 permeance of the
256
membranes at various feed gas pressures up to 15 atm. This was the highest pressure that
membranes could withstand. The possible reason for the collapse of membranes at
pressures beyond 15 atm could be the relatively high D/Δh ratio (D: membrane diameter;
Δh: wall thickness) and its detrimental effect on the mechanical stability of the hollow
fiber membrane as also reported elsewhere [50,51].
It can be found from the results (shown in Figure 6.6) that upon increase in feed
gas pressure, the CO 2 permeance of the hollow fibers is gradually decreased. This trend
can be attributed to the saturation of Langmuir sites. However, it also indicates the
prevalence of a good resistance against plasticization in the fabricated membranes.
Figure 6.6. The trend of changes in CO 2 permeance as a function of upstream pressure
for silicone rubber coated dual-layer hollow fiber membranes.
Y
CO2 permeance (GPU)
CO2 permeance (GPU)
Feed gas pressure (atm)
257
According to the literature [52,53], dense flat membranes prepared from Matrimid tend to
plasticize at pressures around 12–15 atm; witnessed by an upward reflection in the
membrane’s permeability. This is in addition to the fact that there exist a number of
studies highlighting the severity of the plasticization in asymmetric hollow fibers
membranes compared to the ones in flat geometry [54–56]. This can mainly be attributed
to the higher vulnerability of the loosely packed structure of the thin dense-selective layer
in hollow fiber membranes toward swelling upon the sorption of CO 2 molecules. In
overall, the anti-plasticization behavior of dual-layer hollow fiber membranes could be
attributed to both (1) an improved microstructural properties evolved in the dense skin
layer and (2) inevitable role of PBI macromolecules in providing an integrated
interpenetration networks through establishment of the strong hydrogen bonding
interactions with Matrimid chains.
6.3.6. The effect of chemical modification on the gas transport properties of dual-layer
Over the years, various kinds of chemical modification techniques have
extensively been used as effective tools for altering the properties of polymeric materials
andmembranesprepared thereof [12,57–60]. For instance, it was demonstrated in our
earlier studies [11,12] that dense flat membranes prepared from PBI/Matrimid blends
underwent significant improvements in separation performance upon application of
cross-linking modification. In this respect, the same approach was extended to this study
in order to examine its viability and effectiveness for hollow fiber membranes. p-
Xylylene diamine (PXDA) is known to be reactive to the carbonyl functional groups
258
present in the chemical structure of Matrimid and thus was selected as the cross-linking
agent for modification of the membranes. Data in Table 6.7 show that the chemical cross-
linking modification greatly affected the properties of the selected membrane even upon
treatment for a very short period of time. Similar phenomena have been reported in the
case of hollow fiber membranes made from 6FDA-2,6-DAT [57]. The gas permeance of
the hollow fiber was reduced, on average about 84–93%, after cross-linking for only 30 s
and resulted in obtaining membranes with improved performance for H 2 /CO 2 separation.
This may clearly highlight the effective role of cross-linking modification on promoting
the diffusivity selectivity through formation of a tighter chain packing, restriction in
mobility and interstitial spaces among the polymer chains present in the dense functional
layer of the membrane. It was also noted that the CO 2 /CH 4 separation performance of the
membranes was negatively affected. Similarly, this could be attributed to the diminished
size-exclusion capability of the membranes for distinguishing the gas molecules with
close kinetic diameters.
Table 6.7. The effect of chemical cross-linking modification and its period on the gas
permeance and separation factor of dual-layer hollow fiber membranes.
Permeance (GPU) Selectivity, α

Sample ID and
Cross-linking period H2 CH4 CO2 H2/CO2 CO2/CH4
Y-0 Sec (pristine sample) 38.67 1.850 5.65 6.85 3.05
Y-30 Sec 6.10 0.187 0.421 14.49 2.25
Y-1.0 min 5.13 0.173 0.368 13.94 2.13
Y-5.0 min 0.562 0.035 0.061 9.21 1.74
Inner dope: Polysulfone, 25 (wt.%) in NMP;
259
In addition, data in Table 6.7 also suggest that prolonging the cross-linking period
had undesirable effects on both gas permeance and selectivity. This could be attributed to
the intensive effect of cross-linking modification on the membrane microstructure
through excessive reduction in the size of free volumes and interstitial distances between
the polymer chains that could create similar degree of hindrance toward the transport of
gas molecules. Interestingly, a comparison between these data and other reported results
[11] on cross-linking of similar membrane materials could imply the important role of
membrane geometry in effectiveness of the modification process. Perhaps, one may be
able to relate the greater yield of cross-linking in hollow fibers, compared to that in dense
flat membranes, to the higher surface area per unit volume of membranes, easier swelling
of the thinner dense skin layer and its promoting effect on the penetration of the cross-
linking agent into the membrane structure.
6.4 CONCLUSIONS
Following conclusions could be drawn from this study:
1. Novel and high performance dual-layer hollow fiber membranes were
successfully developed by using a polymer blend as the functional material. The
emergence of the two distinct morphologies for inner and outer layers was attributed to
various factors including the characteristics of dope constituents, their composition and
the materials’ chemistry in the course of the phase inversion.
2. The delamination-free structure of the membranes was mainly attributed to the
good miscibility among PBI and Matrimid chains provided by the strong hydrogen
260
bonding, the interpenetration of the solvents and polymeric chains at the interface via
interdiffusion and close solubility parameters between the inner and outer-layer dopes.
3. The separation performance of the hollow fiber membranes was found to be
highly influenced by the type of spinning (i.e., wet-spun/dry-jet) and also the air-gap
distance. The enhanced permeance and selectivity of the membranes, especially in case of
H 2 /CO 2 , at elevated air-gaps could be attributed to the enlarged interstitial spaces
between the polymer chains and the increased intensity in orientation degree of chain
packing induced by the gravitational forces. These were in addition to the possible effect
of shear and elongational forces on the interaction and configuration of the blend chains.
4. The application of the elongational drawing influenced the transport properties
of the dual-layer membranes in almost a similar manner to the increase in the air-gap
distance, but with greater impacts on CO 2 /CH 4 separation performance. This was mainly
attributed to the additional effects of the elongational drawing on the membrane’s outer-
lay microstructure through creating elongated pores in the direction parallel to the
induced forces with resultant hindrance to the passage of methane molecules with
polyhedral structure.
5. The increase in outer dope flow rate could considerably improve the CO 2 /CH 4
separation performance of the membranes, through at the expense of the permeance. The
observed effects were attributed to the formation of a thicker dense skin layer and also
higher degree of molecular orientation and chain packing at the outermost skin induced
by high shear stress.
6. Majority of the hollow fiber membranes exhibited a very good resistance
toward the CO 2 -induced plasticization notably attributed to both the improved
261
microstrucural properties evolved in the dense skin layer and also inevitable role of PBI
macromolecules in providing an integrated interpenetration networks through strong
hydrogen bonding interactions with Matrimid chains.
7. Chemical cross-linking modification was found effective in promoting the
diffusivity selectivity of dual-layer membranes only if applied for a very short period of
time. As a result, H 2 /CO 2 selectivity of dual-layer hollow fiber membranes could be
boosted up to about 14.49.
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269
CHAPTER SEVEN
CONCLUSIONS AND RECOMMENDATIONS
7.1 CONCLUSIONS
In recent years, current available membrane materials have reached Robeson’s
upper bound trade-off limit. Therefore, both the development of membranes materials
with superior separation properties for gas separation and the innovation of membrane
fabrication technology are research-intensive, aimed to produce high performance
membranes that can accomplish/conquer the separation challenges. Accordingly, an
investigation of membrane materials and fabrication based on commercially available
polyimides for variety of gas separation applications including but not limited to He/N2,
H2/N2, H2/CO2, H2/CH4, CO2/CH4, N2/CH4) was carried out in this research study
encompassing four diverse aspects listed below:
1. Development of nanocomposite membranes using MgO nanoparticles with
enhanced gas separation performance
2. Development of high performance membranes for hydrogen separation and
purification from the miscible polymer blends with interpenetration networks
3. Development of carbon molecular sieve membranes from the blends of high
performance materials N2/CH4 and CO2/CH4 separation and hydrogen
purification
270
4. Development of novel high-performnce gas separation membranes through
integration of polymer blending and dual-layer hollow fiber spinning process
The results obtained from these research studies provided further insights on the
important aspects of the gas separation membranes. The following discussions provide a
summary of conclusions derived from these studies.
7.1.1 Enhanced Gas Separation Performance of Nanocomposite Membranes Using
Mgo Nanoparticles
Nanocomposite membranes were fabricated for gas separation applications by the
introduction of magnesium oxide nanoparticles into the Matrimid polymer matrix. The
increase in particle content brought about increments in membrane’s permeability. This
was also accompanied by drops in gas selectivity attributed to the fact that the average
pore size of MgO (30 Å) was much larger than the kinetic diameters of gas molecules. It
was found that heat treatment of the membranes can influence their transport properties
differently. Heat treatment at temperatures below T g reduced the membranes’
permeability, whereas, heat treatment at temperatures exceeding the polymer T g resulted
in membranes with enhanced permeability. Further increments in membrane’s
permeability could be accomplished by quenching the membranes instead of natural
cooling. These phenomena were attributed mainly to the role of fractional free volumes in
the polymeric matrix of membrane.
271
Silver treatment was employed in order to tailor the performance of membranes.
Characterization of membranes revealed that in contrast to the polymeric membrane,
nanocomposite membranes had been impregnated through the adhesion of Ag cations
onto the surface of MgO nanoparticles. The adsorption process was confirmed by
different techniques and oxygen sites at the surface of MgO were recognized to be
responsible for this process. The amount of adsorption was monotonically increased with
the retention time. As a result, silver treated nanocomposite membranes exhibited
improved gas separation performances. Particularly, the H 2 /N 2 and CO 2 /CH 4 selectivity
of nanocomposite membranes after 10-day silver treatment improved to about 146.5 and
42.3, respectively; corresponding to 35% and 50% improvements compared to their
pristine sample.
The effective role of silver ions was recognized to be covering the porous
structure and control of the pore size of MgO nanoparticles. As a result, in addition to
the solution-diffusion mechanism, the size exclusion mechanism at MgO-Ag+ structures
as well as the presence of facilitated transport due to special interaction between CO 2 and
MgO were suggested by experimental analyses to be the governing mechanisms in the
superior separation performance of the newly developed Matrimid-MgO-Ag+
nanocomposite membranes. To our best knowledge, this is the first study that combines
the synergistic features of nanocomposite structure and facilitated transport mechanism
into one membrane by using unique characteristics of MgO for gas separation.
272
7.1.2 Hydrogen Separation and Purification in Membranes of Miscible Polymer
Blends with Interpenetration Networks
It was found in the course of this study that blend membranes prepared by mixing
PBI and Matrimid were completely miscible in molecular level for the wide range of
compositions. The miscibility of these components was largely attributed to the presence
of strong hydrogen bonding interactions between the functional groups. Analysis of the
transport properties of the blend membranes revealed that incorporation of PBI brought
about improvements in gas separation performance of membranes compared to the one
prepared from pure Matrimid. The effect was attributed to the increase in chain packing
density and hindrance in segmental mobility of polymer chains and the subsequent effects
on the diffusivity selectivity of the membranes. This was confirmed by characterization
of the microstructure of membranes.
The separation performance of the membranes was further ameliorated through
chemical modification of blend constituents. Modification of PBI phase with p-
xylenedichloride brings about slight improvements in selectivity performance, especially
for H 2 /CO 2 and H 2 /N 2 . In contrast, the selectivity of membranes was improved
significantly after cross-linking Matrimid with p-xylenediamine. The Matrimid/PBI
(25/75 wt.%) blend membrane cross-linked with p-xylenediamine exhibited the best
separation performance for hydrogen with H 2 /CO 2 selectivity of about 26. The higher
tendency of Matrimid toward cross-linking reaction contributes more in controlling the
transport properties of membranes through diffusion coefficient by increase in chain
packing density and diminishing of excess free volumes.
273
In overall, this study demonstrated successful implications of blending technique
cum chemical modification for the fabrication of high performance polymeric membranes
for gas separation applications. The effect of variation in composition on miscibility and
microstructure, gas permeability and selectivity of blend membranes were investigated.
The results obtained in this study revealed the promising features of developed
membranes for gas separation applications with great potential for hydrogen separation
and purification on industrial scale. To our best knowledge, this is the first study focusing
the exploitation of unique properties of blending high performance polymers of Matrimid
and PBI for the development of specialty membranes for hydrogen separation and
purification.
7.1.3 Carbon Membranes from Blends of PBI and Polyimides For N 2 /CH 4 and
CO 2 /CH 4 Separation and Hydrogen Purification
Carbon molecular sieving membranes developed from the blend of PBI and
various polyimides were analyzed on their potentials for various gas separation
applications. Polymeric films fabricated from blending Matrimid, P84 and Torlon with
PBI were found homogenous in nature and exhibiting desirable gas transport properties.
Therefore, these membranes could be considered as viable precursors for further
development and derivation of carbon membranes. It was realized by comparing the
performance of the carbon membranes prepared at different temperatures that the final
temperature can greatly influence the efficiency of the membranes for their gas
separation. The results suggested achieving a better performance at elevated
temperatures. This was mainly ascribed to the extent of progress in carbonization which
274
could bring about microstructures with higher carbon concentrations and more effective
pore sizes with fine distributions.
All derived carbon membranes demonstrated higher gas permeability compared to
their respective precursors. More interestingly, precursors with tighter polymeric
microstructures where found to offer carbon membranes with higher permeability. It was
found that carbon membranes derived from PBI/Matrimid (50/50 wt. %) exhibited more
attractive performance than the carbon membrane derived from other blends. Further
investigations on this promising blend system revealed the higher Matrimid content could
bring about improved permeability and selectivity particularly for separation of N 2 and
CO 2 from CH 4 .
Chemical modification of PBI/Matrimid precursors prior to carbonization
produced membranes with enhanced performance for separation of H 2 molecules from
N 2 and CO 2 . The results suggested that carbon molecular sieve membranes developed in
this study surpass various trade-off lines and are of great potentials for industrial
applications.
Developed membranes are amenable to surpass several separation performance trade-offs
with great potentials for various industrial applications including CO 2 /CH 4 (α=203.95),
H 2 /CO 2 (α=33.44) and particularly N 2 /CH 4 separation with unprecedented high
permeability (PN2 =2.78 Barrer) and selectivity (α=7.99) for this gas pair. To our best
knowledge, this is the highest ever reported selectivity for this gas pair. In addition,
tuning the PBI content could diversify the application and offer attractive membranes for
275
separation of other important gas pairs.
The results of this research study accentuated the necessity and importance of
adopting a proper strategy in exploiting synergistic beneficial features of advanced
materials (PBI), technology (polymer blending), process (carbonization) and modification
techniques (cross-linking) toward achieving membranes with desired performance.
7.1.4 Development of Novel High-performance Gas Separation Membranes
Through Integration of Polymer Blending Technology and Dual-layer
Hollow Fiber Spinning Process
Dual-layer hollow fiber membranes were successfully fabricated by suing a
polymer blend as a functional material as the outer layer. The effect of various spinning
parameters including the air gap distance, elongational drawing outer dope flow rate on
the morphological evolution, transport properties and separation performance of the
hollow fiber membranes were investigated.
The emergence of these two distinct morphologies for inner and outer layers was
attributed to various factors including the dope constituents, their composition and the
effect of coagulants and the chemistry of materials. A general increasing trend in the gas
permeance of the hollow fiber membranes could be established as a result of increase in
the air gap distance. Similar effects were caused by the application of elongational
drawing. Neither spinning at high air gap distance and application of elongational
276
drawing during the spinning could affect the state of macrovoids in inner layer, most
probably due to the low viscosity of the inner dope. However, the microstructure of the
outer layer was greatly affected and brought about significant improvements separation
performance of the hollow fiber membranes. The silicone rubber coated hollow fiber
membrane spun at the air gap distance 3 cm exhibited the H 2 /CO 2 selectivity of 11.11.
Similarly, silicone rubber coated hollow fiber membrane spun with elongational drawing
exhibited the CO 2 /CH 2 selectivity of 41.81.
Increase in outer dope flow rate was found to result in membranes with
diminished gas permeance accompanied with improvements in CO 2 /CH 4 separation
performance of the membranes. Majority of the hollow fiber membranes exhibited a very
good resistance against the CO 2 -induced plasticization. Additionally, chemical cross-
linking for short period of time was found effective in boosting the selectivity of
membranes for H 2 /CO 2 separation, though at the expense of the gas permeance.
7.2 RECOMMENDATIONS FOR FUTURE WORK
Based on the obtained experimental results, presented discussions and drawn
conclusions from this research study, the following recommendations may provide
further insights for future investigations related to the development of membrane
materials with potentially high-separation characteristics and further advancement of
membrane fabrication technology.
277
7.2.1 Nanocomposite Membranes
The research work presented here on nanocomposite membranes was originated
by the idea of exploiting the unexplored microstructural and surface properties of metal
oxide nanoparticles for enhanced gas separation applications. The development of
successful nanocomposite membranes from such materials in fact opens new doors for
further research on the use of various metal oxides with special inherent and surfacial
properties.
It was revealed in the course of this study that further post-modifications were
required in order revitalize the separation performance of the as-fabricated
nanocomposite membranes. This was mainly attributed to the relatively large pore size of
the magnesium oxides compared to that of gas molecules. The future study may focus on
the careful selection of metal oxide nanoparticles with more suitable pore sizes that fall
within the range the kinetic diameter of gas molecules. This may even eliminate the need
for further modification (e.g., heat treatment, silver ion treatment) of nanocomposite
membranes. Another interesting are of investigation may include the use of other high
performance polymers as the matrix for inclusion of nanoparticles. In this case, special
affinities and interactions between the polymers and nanoparticles may come
advantageous. It can also be interesting to apply surface modification or functionalization
techniques in order to tailor the properties of the nanoparticles.
Considering the silver ion treatment, effect of variation in the concentration of the
metal ion solution may also need to be explored. Besides the heat treatment and silver ion
278
modifications used in this research study, it would also be valuable to use other
modification techniques to tailor the transport and separation performance of
nanocomposite membranes. For examples, chemical cross-linking modification may be
used in order to modify the properties of nanocomposite membranes. The presence of the
nanoparticles inside the polymeric matrix may enhance the intrusion of cross-linking
agents into the membrane structure and facilitate the chance for internal modification in
addition to the surfacial modification.
It also would be worthwhile to examine the long term performance of the
membranes for gas separation especially in terms of their stability and also interaction
between the magnesium oxides and the metal ions used for their modification. Further
investigations may be required in order to examine and identify the role of individual
governing transport mechanisms hypothesized for the performance of the developed
nanocomposite membranes.
7.2.2 Polymeric Blend Membranes
The promising results presented here based on the membranes developed from the
blend of high polymeric material may highlight great potentials for research in this area.
Therefore, future studies may consider investigation for identification of potential
polymeric pairs from high performance materials that can form miscible blends in
molecular level. This also may include trials of novel synthesized polymers. Other
techniques such as enhancement in miscibility through addition of compatiblizers may
apply to those blends in the level of partial miscibility.
279
Due to the promising features of the PBI, it is highly recommended that future
studies focus on further exploitation of this high performance polymer. For example,
other successful candidates for gas separation such as 6FDA-based polyimides, P84 etc,
may also be explored for blending with PBI.
Specifically on the blends of PBI and Matrimid, one area of investigation may
include further amelioration of performance and separation efficiency of the membranes
through the use of other modification. For example, other types of chemical cross-linking
agents varying in chemical structure (aliphatic- or aromatic-based), functional groups,
size, pendants, etc may be used. In addition, effort on the improvements of cross-linking
modifications process would be valuable. In this respect, the primary areas of focus may
include reduction in reaction time and enhancement in reaction efficiency and effect of
concentration. Research on the possible ways to accelerate the cross-linking reaction may
enhance its applicability for industrial practice. In addition, it would be worthwhile to
investigate the possible means to further extend the cross-linking domain from the
surface. Advanced modification approaches may be envisaged to promote cross-linking
to the entire membrane structure.
The developed polymeric blend of PBI/Matrimid at different compositions, can
itself be considered as a material of choice for development of other types of membranes
such as nanocomposite membranes. The areas of application may be extended for
separation of other gases or examined for other membranes-based separation processes.
280
7.2.3 Carbon Membranes from Polymer Blends
The promising results of our research on development of carbon membranes from
miscible blends of polymeric materials provide a viable platform for further studies in
this area. In general, yet more fundamental research studies are required for further
understanding on the preparation of carbon molecular sieve membranes through
carbonization since it involves many complexities. Some of the parameters such as the
effect of final temperature, and profile were studied in the course of this research, but
other areas are suggested to be considered for further investigations. For example,
knowledge about the material degradation, carbon yields and emergence of the
microstructure are worthwhile to be further explored.
The influence of operating temperature and pressure on the gas transport
properties of the carbon molecular sieve membranes is recommended for further studies.
Efforts also worth on getting better insights on the governing transport mechanisms in
carbon molecular sieve membranes. Especial attentions may need to be paid to
differentiation of the roles of entropic and energetic selectivities.
Considering the polymer blend used in this study as the precursor, use of other
modification methods is suggested in order to investigate their effects on the gas
separation performance of the resultant carbon membranes. Further developments would
be valuable on transforming the carbon membranes into the hollow fiber geometry which
is more favorable for industrial applications.
281
7.2.4 Dual-layer Hollow Fiber Membranes from Polymeric Blends
Hollow fiber membranes are more advantages for industrial applications largely
due to their high surface area per unit volume of membrane module. Therefore, this area
has attracted many attentions for further research. One of the key developments made in
the course of this research was the pioneering integration of polymer blending technology
into dual-layer hollow fiber spinning. Therefore, it is highly recommended for future
research to further develop the technique and try on the other materials.
One of the important areas of research may be optimization of the geometry of the
hollow fibers through using different spinneret. Improvement in the mechanical stability
of the membranes can make great impacts on the long term performance of the
membranes and also their resistance to high feed pressures. In addition, further research
may be required to improve the morphological characteristics of the hollow fibers
especially in their inner layer. Various methods such as using alternative materials,
changes in rheological properties of the polymer, changes in bore fluid characteristics, etc
can be examined in this respect in order to reduce or eliminate the macrovoids in the
inner layer.
It is suggested that future studies on the developed membranes explore the
application of these membranes for separation of other gases. Another interesting area is
investigation on the potential use of dual-layer hollow fiber membranes as precursors for
fabrication of carbon molecular sieve membranes.
282

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MEMBRANES AND MATERIALS FOR SEPARATION AND

PURIFICATION OF HYDROGEN AND NATURAL GAS

SEYED SAEID HOSSEINI

NATIONAL UNIVERSITY OF SINGAPORE

PURIFICATION OF HYDROGEN AND NATURAL GAS

SEYED SAEID HOSSEINI

(B. Sc., Chemical Engineering, Isfahan University of Technology)

FOR THE DEGREE OF DOCTOR OF PHILOSOPHY

DEPARTMENT OF CHEMICAL & BIOMOLECULAR

NATIONAL UNIVERSITY OF SINGAPORE

working with great number of people whose contributions to this accomplishment

gratitude to all of them herein:

and valuable contributions in various stages of the research works.

Many thanks go in particular to Prof. K (William B. Krantz). I am much indebted to him

to be members of the examining committee.

assistance, especially at the later stage of my studies.

I was extraordinarily fortunate in receiving wonderful supports from Dr. A. Zadhoush,

teachings, trusts and encouragements. Thank you.

I gratefully acknowledge the International Graduate Scholarship (IGS) offered by Agency

for Science, Technology & Research (A*STAR) which provided me wonderful

opportunity pursue my graduate studies at the National University of Singapore (NUS)

through which I could realize abilities and discover other capabilities.

environment throughout my studies. I really enjoyed being a research scholar affiliated to

supports enabled this work to be successfully completed.

undoubtedly played an important role in my concurrent progress in both academic and

Where would I be without my family? Words fail me to express my appreciation to my

especially in tolerating several years of my absence in pursuit of knowledge.

anyone in the list.

CHAPTER 1 INTRODUCTION TO GAS SEPARATION MEMBRANES 1

1.1 Historical Developments of Membranes 3

1.2 Industrial Applications of Gas Separation Membrane Technology 6

1.2.1 Hydrogen Separation 11

1.2.2 Air Separation 13

1.2.3 Natural Gas Treatment 14

1.3 Principles of Gas Separation Membranes 15

1.3.1 Membrane Materials 15

1.3.2 Membrane Design and Structures 21

1.3.2.1 Dense Versus Porous Membranes 21

1.3.2.2 Symmetric Versus Asymmetric Membranes 21

1.3.2.3 Dynamic in-situ Membranes 24

1.3.2.4 Liquid Membranes 25

1.3.3 Membrane Module Configurations 25

1.3.3.2 Spiral Wound Modules 27

1.3.3.3 Hollow Fiber Modules 28

1.4 Transport Mechanisms in Gas Separation Membranes 30

1.4.1 Poiseuille Flow 31

1.4.2 Knudsen Diffusion 31

1.4.3 Molecular Diffusion 32

1.4.4 Solution-diffusion model 34

1.4.5 Gas Sorption and Diffusion in Glassy Polymers 34

1.4.6 Free Volume in Glassy Polymers 36

1.5 Research Objectives and Organization of Dissertation 38

CHAPTER 2 STRATEGIES AND APPROACHES IN DEVELOPMENT OF GAS

2.1 Key Limitations of Existing Polymeric Membranes 55

2.1.1 Permeability Versus Permselectivitiy 55

2.1.2 CO 2 -Induced Plasticization and Conditioning 57

2.1.3 Physical Aging 59

2.2 Molecular Design of Polymeric Membranes for Gas Separation 62

2.2.1 Tailoring Pure Polyimide Systems 62

2.2.2 Design of Block Copolymer Systems 70

2.3 Modification of Polymeric Membranes for Gas Separation 71

2.3.2 Hybrid Membranes 74

2.3.3 Thermal Annealing 77

2.3.4 Grafting and Halogenation of Polymer Backbone 79