Xia JZ

POLYMERIC GAS SEPARATION MEMBRANES FOR
CARBON DIOXIDE REMOVAL
XIA JIAN ZHONG
(B. S., Peking University, P. R. China)
A THESIS SUBMITTED FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
NUS Graduate School for Integrative Sciences and
Engineering
NATIONAL UNIVERSITY OF SINGAPORE
NOV 2012
To my parents and my wife for their understanding and support without any hesitation
Especially to my father for his selfless love until he left this world
ACKNOWLEDEGMENTS
I wish to take this opportunity to express my sincere appreciation to all the
contributors during my years in the National University of Singapore and University
of Texas at Austin. First of all, I am especially grateful to my supervisors, Professor
Neal Chung Tai-Shung and Professor Donald R. Paul, who have not only provided
guidance during my research activities but have also given generously of their time to
offer encouragement, advice and support. Their pursuance for perfection in research
and publication set a great example for my professional career. I also appreciate the
assistance from my TAC members Prof. Hong Liang and Dr. Pramoda Kumai for
their valuable comments and discussions. I would like to acknowledge the NGS
scholarship offered by NUS Graduate School for Integrative Sciences and
Engineering. They provide me lots of chance to attend international conferences,
summer schools and even long period of research exchange. I also wish to express my
recognition to NUS, A*Star and the Singapore National Research Foundation (NRF)
for the financial support that enables this work to be successfully completed.
It has been pleasant to work with people both in Prof. Chungs group in National
University of Singapore and people in Prof. Pauls group in University of Texas at
Austin. I have enjoyed the friendships with all members of these two groups,
especially Dr. Liu Songlin, Dr. Norman Horn, Dr. Xiao Youchang, Dr. Li Yi, Dr.
Rajkiran Tiwari, Ms. Wang Huan, Ms. Zhang Sui, Mr. Chen Hangzheng, Mr. Yin
Hang and many others for many good times, discussion and sharing of technical
i
experience. Special thanks to Ms. Chuan Irene Christina for all her kindest
cooperation and help on my 2+2 exchange programme. I am also indebted to Liu Di,
Zhang Miao, Liu Jingran, Tang Zhao, Chen Xi, Yang Shengyuan for making my
graduate life joyful. Finally, I must express my deepest gratefulness to my family for
their endless support, especially to my dearest fiancee Yaqian for sharing my life in
Singapore.
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TABLE OF CONTENTS
ACKNOWLEDEGMENTS ...................................................................................... i
TABLE OF CONTENTS ........................................................................................iii
SUMMARY ........................................................................................................... ix
LIST OF TABLES .................................................................................................xii
LIST OF FIGURES .............................................................................................. xiv
CHAPTER 1 Introduction........................................................................................ 1
1.1 Membrane Technology for Gas Separations ...................................... 2
1.2 History of Gas Separation Membranes ............................................... 3
1.3 Applications Based on Gas Separation Membranes ........................... 4
1.3.1 Hydrogen recovery ............................................................................. 5
1.3.2 Nitrogen Enrichment .......................................................................... 7
1.3.3 Recovery of Organic Vapor ................................................................ 7
1.3.4 Carbon Dioxide Capture ..................................................................... 8
1.4 Materials for Gas Separation Membranes ........................................ 11
References .......................................................................................................... 17
CHAPTER 2 Background and Approaches ........................................................... 22
iii
2.1 Permeability, Permeance and Selectivity ......................................... 22
2.2 Solubility .......................................................................................... 24
2.3 Fractional Free volume ..................................................................... 26
2.4 Gas Transport in Rubbery Polymers ................................................ 27
2.5 Gas Transport in Glassy Polymers ................................................... 28
2.6 Effect of Temperature ....................................................................... 29
References .......................................................................................................... 30
CHAPTER 3 Materials and Experimental Methods .............................................. 33
3.1 Materials ........................................................................................... 33
3.2 Preparation of Dense Membranes..................................................... 35
3.2.1 Preparation of Glassy Thick Membranes ......................................... 35
3.2.2 Preparation of Organic-Inorganic Membranes (OIMs) .................... 36
3.3 Preparation of Polymeric Thin Films ............................................... 39
3.4 Characterization of Physicochemical Properties .............................. 41
3.4.1 Measurement of Gel Content ............................................................ 41
3.4.2 Fourier Transform Infrared Spectrometer (FTIR) ............................ 42
3.4.3 Transmission Electron Microscopy (TEM) ...................................... 42
3.4.4 Thermogravimetric Analysis (TGA) ................................................ 42
iv
3.4.5 Wide Angle X-ray Diffraction (WAXD).......................................... 43
3.4.6 X-ray Photoelectron Spectrometer (XPS) ........................................ 43
3.4.7 Elemental Analysis ........................................................................... 43
3.4.8 Nuclear Magnetic Resonance (NMR) .............................................. 44
3.4.9 Simulation Based on Molecular Dynamic ........................................ 44
3.4.10 Variable Angle Spectroscopic Ellipsometer ..................................... 46
3.5 Characterization of Gas Transport Properties .................................. 47
3.5.1 Pure Gas Permeation Tests ............................................................... 47
3.5.2 Mixed Gas Permeation Tests ............................................................ 48
3.5.3 Pure Gas Sorption Tests ................................................................... 48
References .......................................................................................................... 50
CHAPTER 4 Liquid-like Polyethylene Glycol Supported in the Organic-inorganic
Matrix for CO2 Removal .................................................................. 53
Abstract .............................................................................................................. 54
4.1 Introduction ...................................................................................... 55
4.2 Results and Discussion ..................................................................... 60
4.2.1 Basic Physicochemical Properties .................................................... 60
4.2.2 XRD Characterization ...................................................................... 67
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4.2.3 The Gas Permeation Performance .................................................... 68
4.2.5 Effect of Testing Temperature .......................................................... 77
4.2.5 Effect of PEGs Molecular Weights ................................................. 81
Summary ............................................................................................................ 85
References .......................................................................................................... 87
CHAPTER 5 The Effect of End Groups and Grafting on the CO2 Separation
Performance of Polyethylene Glycol Based Membranes ................. 96
Abstract .............................................................................................................. 97
5.1 Introduction ...................................................................................... 98
5.2 Results and Discussion ..................................................................... 99
5.2.1 Basic Physicochemical Properties .................................................... 99
5.2.2 Gas Transport Properties of OIMs with Physical Blending ........... 101
5.2.3 Thermal Properties of GPA1100 Series ......................................... 105
5.2.4 Temperature Dependence of Gas Permeation Properties ............... 107
5.2.5 Thermal Grafting of PEG-azide and Characterizations .................. 112
5.2.6 Gas Permeation Properties After Thermal Grafting ....................... 116
Summary .......................................................................................................... 119
References ........................................................................................................ 121
vi
CHAPTER 6 Aging and Carbon Dioxide Plasticization of Thin Extem XH1015
Polyetherimide Films ...................................................................... 125
Abstract ............................................................................................................ 126
6.1 Introduction .................................................................................... 127
6.2 Results and Discussion ................................................................... 130
6.2.1 Aging Behavior Tracked by Gas Permeation ................................. 130
6.2.2 CO2 Plasticization Pressure Curves ................................................ 135
6.2.3 CO2 Permeability Hysteresis .......................................................... 140
6.2.4 CO2 Permeation Behavior for Short Exposure Times .................... 145
6.2.5 CO2 Permeation Behavior over Long Exposure Times .................. 147
Summary .......................................................................................................... 151
References ........................................................................................................ 153
CHAPTER 7 Gas Permeability Comparison of Extem XH1015 with Polysulfone
and Ultem via Molecular Simulation............................................ 161
Abstract ............................................................................................................ 162
7.1 Introduction .................................................................................... 163
7.2 Results and Discussion ................................................................... 166
7.2.1 Chain Morphology Comparison .......................................................... 166
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7.2.2 Molecular Simulation .......................................................................... 169
Summary .......................................................................................................... 174
References ........................................................................................................ 175
CHAPTER 8 Conclusions and Recommendations .............................................. 177
8.1 Conclusions .................................................................................... 177
8.1.1 Permeability and Selectivity Enhancement by Blending PEG and its
Derivatives .................................................................................................... 177
8.1.2 Permeability Enhancement by Grafting PEG-azide on the Backbone
of OIMs 178
8.1.3 Temperature Effect on Gas Permeability and Selectivity .............. 178
8.1.4 Physical Aging and Plasticization on Polymeric Thin Films ......... 179
8.2 Recommendations .......................................................................... 180
8.2.1 PEG Based Organic-Inorganic Membranes ........................................ 180
8.2.2 Physical Aging and Plasticization Monitored by Gas Permeability .... 181
Appendix A: Structure Determination of Extem XH 1015 ............................... 183
Results .............................................................................................................. 183
References ........................................................................................................ 188
viii
SUMMARY
Membrane technology has been considered as one of the most promising
candidates for selective removal of carbon dioxide from mixture with H2 and N2.
Conventional glassy membranes focused mainly on the size sieving ability of
polymers. Based on the different size of CO2, H2 and N2, the flux order of these
three gases in glassy polymers is usually H2 CO2 N2 and these membranes are
H2-selective. However, the separation mechanism in rubbery membranes,
especially in poly (ethylene glycol) (PEG), is different due to the higher
contribution on solubility selectivity, which means the size sieving effect is not the
dominate factor. Therefore, the flux order of these three gases in rubber is usually
CO2 H2 N2 and these membranes are CO2-selective.
Part of this project focused on exploring the possibility of using favorable
interactions between CO2 and ethylene oxide (EO) groups to improve
permeability/selectivity properties of rubbery membranes. Organic-inorganic
membranes (OIMs) consisting of siloxane network and PEG segments were used
as the substrate. Several PEG and PEG derivatives with different molecular
weight were physically blended into the substrate before the siloxane network was
formed. The membrane containing 60wt% of 1000g/mol PEG could achieve an
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ultra-high CO2 permeability of 845 Barrer with CO2/H2 and CO2/N2 permselectivity
around 10 and 40, respectively. A PEG derivative is blended into the substrate
followed by thermal grafting. Ultra high CO2 permeability (982 barrer at 45 C) is
achieved via physical blending, while extremely high CO2 permeability (1840
barrer at 45 C) is obtained after chemical grafting. Neither of these two
modification methods shows the loss of CO2/H2 and CO2/N2 selectivity compared
to the substrate. Melting and crystallization behaviors of these PEG and PEG
derivatives are believed to significantly affect the overall gas permeation
performance.
Another part of this project focused on glassy membranes, which is also one
of candidates for CO2 removal in industry. However, CO2 plasticization and
physical aging on glassy membranes severely reduced their chances to be further
developed. Industrial glassy gas separation membranes usually have selective
dense layers with thicknesses around 100 nm. It has long been assumed that these
thin layers have the same properties as thick (bulk) films. However, recent research
has shown that thin films with such thickness experience accelerated physical aging
relative to bulk films. Thin films made from Extem XH 1015, a new commercial
polyetherimide, have been investigated by monitoring their gas permeability. The
permeability of the thin films is originally greater than the thick films but eventually
decreases well below the permeability of the thick film. The CO2 plasticization of
x
Extem thin films is also explored using a series of exposure protocols that indicate
CO2 plasticization is a function of film thickness, aging time, exposure time,
pressure and prior history. In order to further explore the structure/property
relationship of glassy polymers, some simulation works based on molecular
dynamics were also conducted.
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LIST OF TABLES
Table 1-1 Most important polymers used in industrial gas separation membrane [10]
.......................................................................................................... 12
Table 1-2 Progress of membranes for the O2/N2 separation (25C) [10] .............. 12
Table 3-1 Chemical structures of polymer used in this study ............................... 34
Table 3-2 Bulk properties of polymers used in this study..................................... 34
Table 3-3 Atom numbers and cell dimensions for PSU, Extem and Ultem
amorphous cells ................................................................................ 46
Table 4-1 Gel content (%) of GP w/o PEG and GPP series .................................. 60
Table 4-2 Thermal properties of GPP series, GP w/o PEG and pure PEGs ......... 62
Table 4-3 Average size and area fraction of silica particles in GP w/o PEG and
GPP1500-60...................................................................................... 67
Table 4-4 Pure gas permeability and selectivity for membranes with different
compositions at 35C ,45C and 55Ca ............................................ 70
Table 4-5 Gas permeability, solubility and diffusivity coefficient results compared
with PDMS and PEO from other sources ......................................... 72
Table 4-6 Mixed gas permeability and selectivity for GPP1000-60 and
GPP1500-60 at 45C ........................................................................ 77
xii
Table 5-1 Thermal properties of GPA1100 series .............................................. 101
Table 5-2 Pure gas permeability and selectivity of OIMs blended with PEG-azide
........................................................................................................ 102
Table 5-3 Solubility and diffusivity coefficients of GPA1100 and GPP1000 series
at 45 C ........................................................................................... 104
Table 5-4 Pure gas permeability and selectivity of GPA1100 series before and after
grafting............................................................................................ 117
Table 7-1 Gas permeation performance of flat dense PSU, Extem and Ultem
membranes ...................................................................................... 167
Table 7-2 Kinetic diameters of various gases ..................................................... 171
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LIST OF FIGURES
Figure 3-1 Synthetic route of Extem XH1015 ...................................................... 33
Figure 3-2 Synthetic route of hybrid membranes ................................................. 37
Figure 4-1 Concept of liquid PEGs supported in the organic-inorganic matrix ... 59
Figure 4-2 STEM images of (a) GPP without free PEG and (b) GPP1500-60 and
(c) EDX analysis of silica particles .................................................. 65
Figure 4-3 STEM images of (a) hybrid membranes and (b) imaginary matrix
constructed with (c) different functional groups .............................. 66
Figure 4-4 STEM images of hybrid membranes after imageJ analysis: (a) GPP
w/o PEG and (b) GPP1500-60.......................................................... 66
Figure 4-5 XRD patterns for (a) GPP400, (b) GPP1000, (c) GPP1500 and (d)
GPP2000 at room temperature ......................................................... 68
Figure 4-6 Selected permeability/selectivity data map for (a) CO2/H2 and (b)
CO2/N2 separation at 35C ............................................................... 69
Figure 4-7 CO2 permeability of GPP series and GP w/o PEG at 35C (blank) and
45C (checked) ................................................................................. 74
Figure 4-8 Permselectivity at 35C (solid) and 45C (hollow) for CO2/H2 .......... 76
xiv
Figure 4-9 DSC curves for (a) GPP400, (b) GPP1000, (c) GPP1500 and (d)
GPP2000 ........................................................................................... 76
Figure 4-10 Change of CO2 permeability of GPP1500-60 from 30C to 55C
80*Tm2o is the onset melting temperature of PEG1500 in GPP1500-60
during 2nd heating. ............................................................................ 80
Figure 4-11 CO2 Sorption isotherm (a) and solubility coefficient (b) of GPP1500 at
35C and 45C .................................................................................. 80
Figure 4-12 Sorption isotherm (a) and solubility (b) of GPP1500, PDMS [52]
semi-crystalline PEO and amorphous PEO [28] at 35C ................. 81
Figure 4-13 Solubility (square) and diffusivity (circle) of hybrid membranes
containing 40wt% of PEG with different molecular weights at 45C
.......................................................................................................... 83
Figure 4-14 Crystallization of PEO segments and PEGs with different molecular
weights .............................................................................................. 84
Figure 5-1 TEM micrography of GP w/o PEG-azide at (a) a low magnitude and (b)
a high magnitude ............................................................................ 100
Figure 5-2 Glass transition temperature shifts of GPA1100 series by DSC ....... 103
Figure 5-3 DSC curves of (a) 2nd heating and (b) 2nd cooling of GPA1100 series
........................................................................................................ 107
xv
Figure 5-4 The temperature dependence of CO2 permeability of GPA1100 series
........................................................................................................ 109
Figure 5-5 Temperature dependences of CO2 sorption isotherms of (a)
GPA1100-20 and (b) GPA1100-40 ................................................ 111
Figure 5-6 Temperature dependence of (a) solubility and (b) CO2 diffusivity of
GPA1100-20 and GPA1100-40 ...................................................... 112
Figure 5-7 Temperature dependence of (a) CO2/H2 and (b) CO2/N2 selectivity of
GPA1100-20 and GPA1100-40 ...................................................... 112
Figure 5-8 13C solid state NMR spectra of (a) GPA1100-40 pristine and (b)
GPA1100-40 after thermal grafting ................................................ 114
Figure 5-9 N1s XPS data before and after thermal grafting for GPA1100-40 ... 115
Figure 5-10 TGA data of GPA1100-40 before thermal grafting ........................ 115
Figure 5-11 CO2 solubility (open) and diffusivity (solid) of GPA1100-40 before
and after grafting ............................................................................ 118
Figure 5-12 Wide angle XRD patterns of GP w/o PEG-azide, GPA1100-40 before
and after the grafting at ambient temperature ................................. 118
Figure 5-13 2nd cooling curve of GPA1100-20 and GPA1100-40 before and after
the grafting ...................................................................................... 119
xvi
Figure 6-1 DSC thermograph showing the glass-transition temperature of Extem
........................................................................................................ 130
Figure 6-2 Oxygen permeability of (a) Extem films with similar thickness and (b)
Matrimid, PSF and Extem films as a function of aging time ......... 131
Figure 6-3 (a) Oxygen, (b) nitrogen, (c) methane permeability of Extem films with
different thickness as a function of aging time ............................... 134
Figure 6-4 O2/N2 selectivity of Extem films as a function of aging time ........... 134
Figure 6-5 CO2 sorption isotherms for thick films at 35C: Matrimid [54], PSF [55],
PPO [56], butyl rubber [53] ............................................................ 137
Figure 6-6 Normalized CO2 permeability of thin films as a function of (a) pressure
(Matrimid, PPO and PSF data are taken from the literature [18]) and (b)
CO2 concentration........................................................................... 139
Figure 6-7 (a) CO2 permeability and (b) normalized CO2 permeability as a function
of CO2 pressure for different aging times ....................................... 140
Figure 6-8 CO2 permeability hysteresis curves of thin films aged (a) 25 hr, (b)
100 hr and 150 hr ............................................................................ 142
Figure 6-9 CO2 permeability as a function of time at (a) 32 atm (after increase CO2
pressure)and (b) 4 atm (after decrease CO2 pressure) during hysteresis
testing.............................................................................................. 144
xvii
Figure 6-11 (a) CO2 permeability and (b) normalized CO2 permeability during
long time CO2 exposure at different pressures ............................... 148
Figure 6-12 (a) CO2 permeability and (b) normalized CO2 permeability as a
function of exposure time at 8 atm for different polymer films ..... 150
function of exposure time at 32 atm for different polymer films ... 151
Figure 7-1 Chemical structures of PSU, Extem and Ultem ................................ 166
Figure 7-2 Chain morphologies of PSU, Extem and Ultem with 5 repeat units . 166
Figure 7-3 Morphology of two polymer chains with 5 repeat units for PSU, Extem
and Ultem ....................................................................................... 169
Figure 7-4 Fractional accessible volumes and relative FAV values of PSU, Extem
and Ultem, probed with different diameters ................................... 170
Figure 7-5 Correlation between gas permeability and 1/FAV ............................ 172
Figure 7-6 FAV ratios of Extem/PSU and Ultem/PSU probed by different
diameters ......................................................................................... 174
xviii
CHAPTER 1 Introduction
Membrane technology covers almost every aspect of separation engineering,
including solid-liquid (microfiltration, ultrafiltration) [1], ion-liquid (nanofiltration
[2], reverse osmosis [3], forward osmosis [4]), liquid-liquid (pervaporation [5]),
liquid-gas (gas contactor [6]) and gas-gas separation (gas separation [7]).
Compared to the convention separation processes, e.g., distillation or extraction,
membrane based separations are generally cost-effective, energy efficient and
environmentally friendly. Moreover, membrane separation units are modular so
that they are easy to install, operate and scale up. For example, the juice
concentration process in food industry is now dominated by membrane technology
due to the ability of membranes to remove water at room temperature [8]. Reverse
osmosis and membrane bioreactors are also very popular processes, especially, in
seawater desalination and waste water treatment, because of their high reliability
and efficiency [9]. However, gas separation membranes are relatively less popular
than other highly competitive technologies. Developing the usage of membranes
in emerging gas separation applications is a must for researchers in this field. In
this introductory chapter, several applications based on gas separation membranes
will be reviewed, and some potential applications in carbon dioxide related
separation will be discussed. Glassy, rubbery and organic-inorganic membranes
1
will be involved in the membrane fabrications and discussions.
1.1 Membrane Technology for Gas Separations
Due to the extremely small size of the separation targets, gas separation
membranes are usually thin selective barriers between two gas phases. The
gradient of the chemical potential due to the different gas concentrations in the
two phases becomes the driving force of gas diffusion across the membrane.
Today, most of gas separation membranes are in the form of hollow fiber modules,
with fewer being formed in spiral-wound modules. The hollow fiber modules are
usually less expensive than the spiral-wound modules, while the latter are usually
considered to be more reliable in terms of easy and cheap maintenance. In
principle, the permeation and separation performance of gas membranes depend
on four parameters [10]: (1) the material, which determines the intrinsic
permeability and separation factor; (2) the membrane structure and thickness,
which determine the permeance; (3) the membrane configuration, e.g., flat sheet
or hollow fiber; and (4) the module and system design. Developing a material into
a commercial product takes years to evaluate and refine the aforementioned
parameters.
2
1.2 History of Gas Separation Membranes
Long before the first commercial gas separation membranes (named Prism)
were introduced, people had already noticed the potential usage of membranes as
gas separation tools. In 1829, Thomas Graham discovered the law of gas diffusion
by using a tube with one end sealed with plaster of Paris [11]. Three years later,
Mitchell [12] reported for the first time that different gas molecules have different
tendencies to pass through rubber membranes, which means the flux of each gas is
different. Since then, lots of polymers have been studied extensively to look for
their potential to be gas separation membranes. H. A. Daynes and R. M. Barrer are
the pioneers in performing quantitative measurements of gas permeability by
using the time-lag method. A number of permeability data had been obtained from
lots of potential membrane materials [13]. However, the lack of technology to
produce high performance and low cost modules postponed the applications of gas
separation membranes, until Loeb and Sourirajan [14] invented a novel phase
inversion method to cast asymmetric cellulose acetate membranes, which enables
the reduction of effective membrane thickness from several micrometers into
sub-micrometer level. The invention of high-flux anisotropic membrane modules
in the forms of spiral-wound and hollow fiber further facilitated the development
of gas separation membranes. In 1980, Permea delivered the first generation
polysulfone hollow-fiber membranes for hydrogen recovery from purge gas
3
steams of ammonia plants. Soon after the success of Permea, Cynara (now part of
Natco), Separex (now part of UOP), and GMS (now part of Kvaerner) had
commercialized cellulose acetate membranes for removing carbon dioxide from
natural gas [15]. More recently, the PolarisTM membrane developed by MTR
(Membrane Technology and Research, Inc.), which is a thin film composite
membrane in spiral wound form, shows a CO2 permeance ten times higher than
the conventional cellulose membranes [16].
1.3 Applications Based on Gas Separation Membranes
Generally speaking, membrane-based gas separation has become more and
more important compared to the conventional gas separation technologies such as
adsorption, absorption and cryogenic distillation [15]. Many common polymer
materials, such as polydimethylsiloxane (PDMS), cellulose acetate (CA),
polysulfone (PSF), polyethersulfone (PES), and polyimide (PI), had been
fabricated into membrane modules and applied to various gas separation processes
such as hydrogen recovery, nitrogen enrichment, recovery of volatile organic
compounds (VOCs), and separation of acid gases in natural gas resources and
steel industries [17].
4
1.3.1 Hydrogen recovery
Hydrogen is one of the most demanded gases in recovery processes due to its
high value and ease of separation. The cost of hydrogen is highly related to energy
prices since hydrogen is mostly produced by reforming natural gas or coal. Since
the oil price increases almost every month in recent years, the importance of
hydrogen recovery is highlighted to reduce the running cost of refinery plants.
Hydrogenation of unsaturated hydrocarbons and hydrotreating to remove sulfur
from fuels are the two major consumptions of hydrogen [18]. During these
processes, purge gases containing a high partial pressure of hydrogen are needed
to remove inert gases from reactors. By using a membrane separation system,
most of the purge hydrogen could be recovered.
Hydrogen is a clean energy carrier that has great potential to replace gasoline,
which could sufficiently reduce the production of greenhouse gases and toxic
exhaust gases. By using hydrogen as the energy resource, fuel cells could directly
generate electricity with water as the only exhaust. The large demand of hydrogen
in the near future requires capacity upgrades of current production plants.
Nowadays, the large industrial scale production of hydrogen occurs via steam
methane reforming (SMR) followed by the water-gas shift (WGS) reaction [19].
These reactions are as follows:
5
m
Cn H m nH 2O nCO ( n) H 2 (1-1)
2
CO H 2O CO2 H 2 (1-2)
Purification technologies are crucial to the a hydrogen economy because the
minimum purity requirement for the fuel cell is higher than 99.99%. To date,
pressure swing adsorption (PSA) and cryogenic distillation are the widely accepted
methods. However, both are energy-intensive processes and only applicable for the
large scale manufacture. Membrane technology offers a bright vision for the
hydrogen purification market because membrane separation has the following
advantages: (1) simple module design and small units, (2) comparative lower initial
investment, (3) simple operation and maintenance, (4) tailored product for
hydrogen purification at different scale and degree.
After SMR and WGS reaction, the major components of the stream are
hydrogen and carbon dioxide. Hydrogen enrichment can be achieved either by H2-
or CO2- selective polymeric membranes. Generally, glassy polymers, especially the
widely used polyimide membranes are H2-selective, while rubbery polymers, for
example, polyethylene oxide membranes are CO2-selective. These two types of
membranes have their own advantages and disadvantages. Thus, the final choice of
the membrane hinges more on the operating parameters and applications.
6
1.3.2 Nitrogen Enrichment
The primary utility for nitrogen is as a protecting inert atmosphere.
Membrane-generated nitrogen could be used onsite anywhere flammable materials
are stored, processed or handled. Many LNG ships, offshore platforms, and
chemical tank farms are supplied with membrane generated nitrogen. Onsite
nitrogen generators are also used in perishable warehouses, cargo containers,
sintered-metal process furnaces, and oil-well servicing [20]. Membrane based
on-board inert gas generation systems are employed in supersonic aircraft, for
example, USA Air Force F-22, where the nitrogen produced from the compressed
air in the jet engine is purged into the fuel tank onboard [21].
1.3.3 Recovery of Organic Vapor
Recovery of organic vapor from off-gas is not only environmentally desirable
but also economically favored. In a PVC (poly (vinyl chloride)) production plant,
valuable compounds, like vinyl chloride monomer, can be recovered [22]. At tank
farms or petrol stations, volatile organic vapors emissions can also be controlled
by membrane separation systems in order to meet the governmental regulations
[23].
7
1.3.4 Carbon Dioxide Capture
Although there is no universal agreement on the cause of global climate change,
the greenhouse gas (GHG), mainly anthropogenic carbon dioxide emission is
considered as the main suspect by the public. According to a report from U.S.
Department of Energy (DOE), approximately 83% of the GHG emission in U.S. is
produced from combustion and nonfuel use of fossil fuels. The capture of CO2
would not only mitigate the global warming concern but would also have some
economic benefits because CO2 could be used for enhanced oil recovery,
enhanced coal bed methane recovery, and etc.
Currently there are three major approaches to reduce CO2 emission from fossil
fuel; these are pre-combustion, oxyfuel and post-combustion [24]. The main
principle of pre-combustion is to supply purified oxidizer and purified fuels to the
combustion turbine in order to minimize the heat loss caused by the inert gases. For
example, in a typical integrated gasification combined cycle power plant (IGCC),
the fuel (coal), is sent to the gasifier to produce hydrogen and carbon monoxide.
Afterwards, more hydrogen is generated by converting carbon monoxide to CO2
by WGS reaction. Before the fuel stream is sent to the gas turbine, the inert CO2
should be removed in order to achieve high electricity generation efficiency.
Because of the high temperature of the mixed steam, the thermal stability of the
8
membrane module becomes critical. A polybenzimidazole (PBI) membrane
developed by Los Alamos National Laboratory has shown long-term hydrothermal
stability at 250 degrees for 400 days [25]. Some ceramic membranes are also
competitive candidates for this high temperature CO2/H2 process [26]. However,
these ceramic membranes only allow hydrogen to pass through, and CO2 remains
in the high pressure retentate stream.
Another promising technology is oxy-combustion, in which the fuel is burned
with almost pure oxygen mixed with the recycled flue gas [27]. The advantage of
this technology is that the exhausts are only CO2 and water, which means the CO2
can be compressed and stored after dehydration without spending energy on other
inert gases (for example, nitrogen). Thus, nitrogen has to be removed from the air
to produce enriched oxygen at the beginning of this process. The conventional way
to remove N2 from air is cryogenic distillation because N2 has higher a boiling
point than O2. However, many attempts have been made to reduce the cost of
oxygen generation by using membranes. Praxair [28] employed an oxygen
transport membrane in the boiler so that oxygen could diffuse directly into the
combustion chamber to burn. The recycled flue gases have to be sent back and
mixed with oxygen and fuel because the combustion furnace cannot withstand the
ultra-high temperature if the fuel was burned with pure oxygen.
9
Post-combustion CO2 capture has the greatest potential to be the near-term
solution for reducing CO2 emission from power plants because this technology can
be retrofitted to the existing IGCC or conventional coal power plant due to the
direct removal of CO2 from flue exhaust [27]. However, lots of challenges have to
be solved. First, the flue gas after combustion is at atmosphere pressure, and the
content of carbon dioxide is only around 10-20%, which means the partial pressure
of CO2 is only 0.1- 0.2 atm [29]. The thermodynamic driving force for CO2 capture
is so low that additional solutions have to be applied. On the other hand, the CO2
captured by the post-combustion is in the low pressure side. Appropriate
compression is needed to meet the sequestration requirements. Meanwhile, the
temperature of flue gas coming from a turbine is higher than 100 C; in that case,
heat exchange or additional cooling treatment is required. Amine-based absorption
system is a mature and commercially available solution for the post-combustion
capture. Amines react with CO2 to form reversible chemicals that could release the
CO2 at higher temperature and lower pressure. The main advantage of the
amine-based system is that this absorption process can capture CO2 at lower
pressure compared to membrane processes [29]. Nevertheless, there are other
problems like scale up, amine losses, degradation and corrosion related amine
absorption. Membrane technology provides a more efficient and user friendly
method that could replace amine-based systems. Firstly, the membrane does not
involve liquid chemicals such as amines that are difficult to handle and maintain.
10
Secondly, the footprint of a membrane separation unit is much smaller than the
amine absorption tower at the same manufacturing capacity. Last but not least,
membrane systems are quite easy to scale up just by employing more membrane
modules. Although membrane based systems still have their drawbacks, like lower
selectivity for CO2, higher capital investment, additional recompression cost and so
on, membrane technology is still a promising solution for the post-combustion CO2
capture; because the cost of membrane modules could be reduced once the
production quantity increases, and the selectivity problem could be solved by
developing new membrane materials or employing multi-stage separation.
1.4 Materials for Gas Separation Membranes
Both glassy and rubbery polymers are used to produce polymeric membranes.
Glassy polymers have mechanical properties that permit them to be used in
self-supported structure like hollow fibers while rubbery materials have to have a
proper support substrate because of their softness. These are some specific
requirements for commercial membrane materials: 1) good mechanical strength; 2)
good chemical resistance; 3) high separation factor with reasonable flux; 4) high
thermal stability; 5) good processability; 6) low cost and environmentally friendly.
Until now, only a few polymers are employed in gas separation membrane as
listed in Table 1-1.

11
Table 1-1 Most important polymers used in industrial gas separation membrane
[10]
Rubbery polymers Glassy polymers

Poly(dimethylsiloxane) Cellulose acetate
Ethylene oxide/propylene oxide-amide copolymers Polyperfluorodioxoles
Polycarbonates
Polyimide
Poly(phenylene oxide)
Polysulfone
For glassy polymers, O2/N2 selectivity is a useful index to evaluate their
separation performance. Table 1-2 indicates the milestones of membrane
development for O2/N2 separation.
Table 1-2 Progress of membranes for the O2/N2 separation (25C) [10]
year polymer O2 permeability O2/N2 selectivity

(Barrer)
1970s Poly(vinyltrimethylsilane) 47 4.3
1982 Poly(4-methyl-1-pentene) 24 3.6
1985 Ethyl cellulose 15 3.4
1986 polysulfone 1.2 6.0
1989 Poly(phenylene oxide) 16 4.0
1989 Halogenated 2.3-1.4 6.4-7.4
polycarbonates (35C)
1996 polyimides 4-0.1 6-9
2005 polyimides 18-0.079 9-19.8
In this dissertation, CO2/H2 and CO2/N2 are the targeted gas pairs to be
separated, so the more interesting materials are rubbery polymers and certain
12
polyimides. Depending on the nature of the material, gas separation membranes
could be classified into two categories: H2 selective or CO2 selective. H2-selective
membranes are common glassy polymers which inherently have better thermal
stability and mechanical property than the rubbery polymers while CO2-selective
membranes are usually made of rubbery materials or organic-inorganic hybrid
materials.
H2-selective membranes are preferred if the ultimate usage of the purified
hydrogen is as an energy resource in a power plant operated at a low pressure of
approximately several bars. The remaining carbon dioxide in the high pressure
retentate stream could be storied for other usage. Therefore, the expensive
recompression of CO2 for sequestration would be reduced. However, most glassy
polymers show a trade-off relationship between gas permeability and selectivity,
and the absolute permeability of glassy polymers is generally smaller than that of
rubbery polymers. Furthermore, plasticization by CO2 can deteriorate the
membrane separation performance by lowering the H2/CO2 selectivity in the mixed
gas compared to that expected from pure gas permeation testing. A great deal of
investigations has been devoted to minimizing the plasticization caused by
condensable penetrants [30-32].
CO2-selective membranes are at preferred when the purified hydrogen is to be

13
employed as a portable vehicle fuel or the feed stock for fuel cell applications. For
CO2-selective membranes, the hydrogen generated by the WGS reactions remains
on the high pressure side so that it can be stored and distributed more effectively
via the existing supply network without additional recompression. Moreover,
because the solubility selectivity is the dominate factor in overall selectivity for
rubbery membranes, CO2/H2 selectivity and CO2 permeability can be
simultaneously improved. Nevertheless, rubbery CO2-selective membranes
perform well only at low temperature, which require more substantial pre-cooling,
e.g., when used in post-combustion CO2 capture. Another potential application of
CO2-selective membranes is to upgrade biogas [33], which requires removal of
CO2 and H2S from CH4 and H2 streams. Rubbery CO2-selective membranes
usually have larger gas flux than the glassy H2-selective membranes when their
selectivity is comparable. Therefore, CO2-selective membranes will yield greater
productivity for hydrogen separation at low pressure and low temperature when the
same membrane area is used. Since the methane and hydrogen gas stream pressure
is low in the case of bio-hydrogen purification, the relatively poor mechanical
properties of CO2-selective rubbery membranes is not a great concern.
1.4 Goals and Organization of the Dissertation
The rising concern of global climate change requires more advanced
technology to control CO2 emission world-wide. Membrane based gas separation

14
is one of the most important technologies for addressing this challenge by
capturing CO2 generated from coal fired power plants. The competition of
membrane technology for CO2/light gas separation with conventional gas
separation technologies relies critically on the gas permeability and selectivity of
the available membrane materials. With extensive experimental studies done on
glassy materials, the structure/property relationship shows a trade-off which may
not provide separation performance good enough for CO2 removal from light
gases. In this project, both rubbery (organic-inorganic hybrid membrane, but
mainly rubbery) and glassy membranes are investigated. The purpose of studying
rubbery membranes was to push the permeability and selectivity to a higher level
without restriction of the usual trade-off relationship; while the works on glassy
polymers were targeted for developing a methodology to monitor the competition
between physical aging and CO2 plasticization. In the meanwhile, some
simulation works were also performed to predict the permeation performance.
Overall, the main goal of this project is to solve the problems associated with
making membrane separations a worthy technology for CO2 capture. The works
done on rubbery materials focus on developing high permeability and high
selective membranes to meet the energy cost requirement of post-combustion CO2
capture when CO2 selective membranes are employed; while the works on glassy
materials attempt to understand the aging and plasticization phenomenon in a very
fundamental way when H2 selective membranes are employed.

15
This dissertation is comprised of eight chapters including their
introductory chapter. Chapter 2 presents the background on gas transport in
polymeric membranes. Chapter 3 describes the materials and experimental
techniques used in this dissertation. Chapter 4 and 5 are focused on developing
new organic-inorganic hybrid membrane materials. Ethylene oxide units are
identified as the key to achieve high CO2 permeability and high CO2 light gas
selectivity simultaneously. Several approaches, including physical blending,
chemical grafting and refining of end groups have been used. Chapter 6 discusses
the accelerated physical aging and plasticization of polymeric thin films in order
to evaluate the permeation performance of glassy membranes more correctly.
Chapter 7 reports some preliminary simulation results on establishing a prediction
methodology of common gas separation materials based on molecular dynamics.
Finally, Chapter 8 presents the conclusions and recommendations for future work.
16
References
[1] M. Cheryan, Ultrafiltration Handbook, Taylor & Francis, 1998.
[2] R. Rautenbach, A. Grschl, Separation Potential of Nanofiltration Membranes,
Desalination, 77 (1990) 73-84.
[3] W. Byrne, Reverse Osmosis: A Practical Guide for Industrial Users, Tall Oaks
Pub., 2002.
[4] T.Y. Cath, A.E. Childress, M. Elimelech, Forward Osmosis: Principles,
Applications, and Recent Developments, Journal of Membrane Science, 281
(2006) 70-87.
[5] X. Feng, R.Y.M. Huang, Liquid Separation by Membrane Pervaporation: A
Review, Industrial & Engineering Chemistry Research, 36 (1997) 1048-1066.
[6] A. Mansourizadeh, A.F. Ismail, Hollow Fiber GasLiquid Membrane
Contactors for Acid Gas Capture: A Review, Journal of Hazardous Materials,
171 (2009) 38-53.
[7] B.D. Freeman, Basis of Permeability/Selectivity Tradeoff Relations in
Polymeric Gas Separation Membranes, Macromolecules, 32 (1999) 375-380.
[8] B. Jiao, A. Cassano, E. Drioli, Recent Advances on Membrane Processes for
the Concentration of Fruit Juices: A Review, Journal of Food Engineering, 63
(2004) 303-324.
[9] J.-J. Qin, K.A. Kekre, G. Tao, M.H. Oo, M.N. Wai, T.C. Lee, B. Viswanath, H.
17
Seah, New Option of MBR-RO Process for Production of Newater from
Domestic Sewage, Journal of Membrane Science, 272 (2006) 70-77.
[10] P. Bernardo, E. Drioli, G. Golemme, Membrane Gas Separation: A
Review/State of the Art, Industrial & Engineering Chemistry Research, 48
(2009) 4638-4663.
[11] E.A. Mason, From Pig Bladders and Cracked Jars to Polysulfones: An
Historical Perspective on Membrane Transport, Journal of Membrane Science,
60 (1987) 125-145.
[12] J.V. Mitchell, J. R. Inst., 101 (1831).
[13] D.R. Paul, Y.P. Yampolskii, Polymeric Gas Separation Membranes, CRC
Press, 1994.
[14] S. Loeb, The Loeb-Sourirajan Membrane: How It Came About, in:
Synthetic Membranes:, American Chemical Society, 1981, pp. 1-9.
[15] R.W. Baker, Future Directions of Membrane Gas Separation Technology,
Industrial & Engineering Chemistry Research, 41 (2002) 1393-1411.
[16] N. Du, H.B. Park, M.M. Dal-Cin, M.D. Guiver, Advances in High
Permeability Polymeric Membrane Materials for CO2 Separations, Energy &
Environmental Science, 5 (2012) 7306-7322.
[17] R.W. Baker, Membrane Technology and Applications, J. Wiley, 2004.
[18] S.P. Nunes, K.V. Peinemann, Membrane Technology in the Chemical Industry,
in, Wiley-VCH, Weinheim, Germany, 2006.

18
[19] L. Shao, T.S. Chung, In Situ Fabrication of Cross-Linked PEO/Silica
Reverse-Selective Membranes for Hydrogen Purification, International Journal
of Hydrogen Energy, 34 (2009) 6492-6504.
[20] D.J. Stookey, Gas-Separation Membrane Applications, in: Membrane
Technology, Wiley-VCH Verlag GmbH & Co. KGaA, 2006, pp. 119-150.
[21] V.P. Crome, A.J. Yoder, Air Separation Module Using a Fast Start Valve for
Fast Warm up of a Permeable Membrane Air Separation Module, in, Google
Patents, 2002.
[22] R.J. Lahiere, M.W. Hellums, J.G. Wijmans, J. Kaschemekat, Membrane
Vapor Separation. Recovery of Vinyl Chloride Monomer from PVC Reactor
Vents, Industrial & Engineering Chemistry Research, 32 (1993) 2236-2241.
[23] W.H. Koch, Developing Technology for Enhanced Vapor Recovery: Part 1
Vent Processors, Petroleum Equipment & Technology, (2001) 16-22.
[24] B. Metz, I.P.o.C.C.W.G. III., IPCC Special Report on Carbon Dioxide
Capture and Storage, Cambridge University Press for the Intergovernmental
Panel on Climate Change, 2005.
[25] K.A. Berchtold, Novel Polymeric-Metallic Composite Membranes for CO2
Separation at Elevated Temperatures. , in: American Filtration and Separation
Society Fall Topical Conference, Pittsburgh, PA 2006.
[26] S. Smart, C. Lin, L. Ding, K. Thambimuthu, J.C.D. Da Costa, Ceramic
Membranes for Gas Processing in Coal Gasification, Energy Environmental

19
Science, 3 (2010) 268-278.
[27] T.C. Merkel, H. Lin, X. Wei, R. Baker, Power Plant Post-Combustion Carbon
Dioxide Capture: An Opportunity for Membranes, Journal of Membrane
Science, 359 (2010) 126-139.
[28] M.M. Shah, van Hassel, B., Christie, M., Li, J., CO2 Capture by Membrane
Based Oxy-Fuel Boiler. , in: Proceedings of the 2006 Conference on Carbon
Capture and Sequestration, Alexandria, VA, 2006.
[29] E. Favre, Carbon Dioxide Recovery from Post-Combustion Processes: Can
Gas Permeation Membranes Compete with Absorption?, Journal of Membrane
Science, 294 (2007) 50-59.
[30] T.S. Chung, J. Ren, R. Wang, D. Li, Y. Liu, K. Pramoda, C. Cao, W.W. Loh,
Development of Asymmetric 6FDA-2, 6DAT Hollow Fiber Membranes for
CO2/CH4 Separation: Part 2. Suppression of Plasticization, Journal of
Membrane Science, 214 (2003) 57-69.
[31] C. Cao, T.S. Chung, Y. Liu, R. Wang, K. Pramoda, Chemical Cross-Linking
Modification of 6FDA-2, 6-DAT Hollow Fiber Membranes for Natural Gas
Separation, Journal of Membrane Science, 216 (2003) 257-268.
[32] J. Wind, C. Staudt-Bickel, D.R. Paul, W.J. Koros, The Effects of Crosslinking
Chemistry on CO2 Plasticization of Polyimide Gas Separation Membranes,
[33] S. Basu, A.L. Khan, A. Cano-Odena, C. Liu, I.F.J. Vankelecom,

20
Membrane-Based Technologies for Biogas Separations, Chemical Society
Review, 39 (2010) 750-768.
21
CHAPTER 2 Background and Approaches
2.1 Permeability, Permeance and Selectivity
There are three basic technical terms used to describe the performance of
membranes: permeability coefficient, permeation rate, and separation factor.
Permeability and separation factor are intrinsic properties of the membrane
material, while permeance is thickness dependent. Permeance is used to
characterize composite membranes consisting of a porous supported layer and a
non-porous thin layer whose thickness cannot be measured very accurately. The
permeation rate is expressed as cm3(STP)/cm2scmHg, whose units, indicate the
permeation rate should be the volume of gases that pass through the membrane per
area per second at unit pressure. The term permeability is mainly used here for
dense, or nonporous membranes, that function by a solution-diffusion mechanism
[1, 2] to describe the transport process. In a typical gas permeation testing, the feed
gas at the high pressure (pu) side will dissolve into the upstream surface of the film,
diffuse through the polymer because of the different gas partial pressures in the
upstream and downstream, and will finally desorb from the downstream side of the
film. This movement in one dimension could be described by the Ficks law in the
form of flux in x direction:
22
Dl dC
N (2-1)
1 w dx
where N is the flux along the x-direction, Dl is the gas local diffusion coefficient, C
is the local concentration of dissolved gas, w is the weight fraction of gas in the
film.
The steady state permeability through a thin film of thickness l is defined as [3,
4]:
N l
P (2-2)
pu pd
where pu and pd are the upstream pressure and downstream pressure, respectively. If
we put eq 2-1 into eq 2-2 and integrate from x = 0 (C = Cu) to x=l (C = Cd), one
obtains:
Cu C d
PD (2-3)
pu p d
where D is the concentration averaged effective diffusion coefficient in the range
from Cd to Cu:
1 Cu Dl 1 Cu
D
Cu C d Cd 1 wdC Cu Cd
Cd
Deff dC (2-4)
and Deff is the local effective diffusion coefficient.
In a typical gas permeation test, the upstream pressure is much higher than the
downstream pressure. In this case, both pd and Cd could be ignored, and eqs 2-3
23
reduces to:
P D S (2-5)
where S is the apparent sorption coefficient or the solubility of gas in the polymer at
the upstream pressure.
Cu
S (2-6)
pu
The ideal selectivity of membranes for pure gases A and B is defined as follows:
PA D A S A
A, B (2-7)
PB DB S B
where overall selectivity could be divided into diffusivity selectivity and solubility
selectivity.
2.2 Solubility
The solubility of a gas in a polymer can be determined directly by measuring
the weight increase at certain gas pressure. The solubility of gas A in a polymer
depends on the nature of the polymer, its prior history in some cases, and
conditions of measurement such as the temperature. The dual mode sorption model
is the most commonly used one to describe the sorption of small molecules in
glassy polymer materials. It combines the independent processes that follow a
simple Henrys law form with Langmuir-type sorption. Henrys law sorption, is
observed in liquids and rubbery polymers and reflects a simple solubility

24
phenomenon. The Langmuir sorption is a non-equilibrium process, with a finite
capacity, associated with the excess free volume of the glassy polymer. The Henry
sorption can be described using the same equation as in the liquid:
C D ( p) k D p (2-8)
where CD ( p) is the gas concentration in the polymer at pressure p, kD is the Henrys
law constant.
The Langmuir sorption could be roughly classified as a hole filling process.
Small penetrants keep adsorbing and desorbing at a rate b and finally reach dynamic
equilibrium. This movement could be depicted as:

C H bp
C H ( p) (2-9)
1 bp
Overall, the sorption in the glassy polymer could be expressed as the combination
of above two types of sorption:
C H bp
C ( p) C D C H k D p (2-10)
1 bp
When the pressure is low, there is a steep increase of the sorption isotherm curve
due to the hole filling process. After these holes are saturated, the Henrys law
sorption dominates so that the slope of sorption curve becomes constant. For the
rubbery polymers, like polyethylene oxide, Henrys law describes the gas sorption
isotherms.
25
2.3 Fractional Free volume
Polymer scientists have made significant attempts to theoretically predict the
intrinsic permeability of polymers according to monomer moieties, chain structures
and rigidity, and functional groups [5]. Salame [6] developed the so-called
Permachor method to forecast oxygen permeability in barrier-type polymers via
the calculation of an empirical factor for each chemical group which contributes to
the total permeability. Bicerano [7] proposed the use of packing density, cohesive
energy and rotational freedom of a polymer as important parameters to predict
permeability. However, the method developed by Lee [8] to correlate gas
permeability with free volume has received great attention and acceptance. The free
volume concept proposed by Lee was defined as (V-Vo), where V is the specific
volume obtained experimentally, while Vo is taken as 1.3 times of Vw which is the
sum of van der Waals volume of the groups calculated following the Bondis
method [9] or Park & Pauls method [10]. Extensive experiments suggest that the
effects of polymer structure on P is much more the result of varieties in the
diffusion coefficient (D) rather than solubility coefficient (S) [11].
Though many parameters affect the diffusion coefficient, the free volume plays
a much more crucial role than others. Thus, a highly simplified but very effective
relationship between the permeability coefficient and the free volume has been
26
established through experiments [12]:
P = A exp (-B/FFV) (2-11)
where A and B are constants for a particular gas, while FFV is the abbreviation of
fractional free volume defined as following.
FFV = (V-Vo)/V (2-12)
The FFV value can be theoretically estimated from the molecular structure with the
aid of the compass force field theory [13].
2.4 Gas Transport in Rubbery Polymers
Gas permeation in rubbery polymers is well understood in terms of the
solution-diffusion model. The sorption of gases in rubbery materials is the same as
in low molecular weight liquids and generally obeys Henrys law. So under a
certain pressure, the permeation rate is controlled by the diffusion step and could
be satisfactorily described by Ficks law [14]. In a rubbery polymer, the segments
of the polymer backbone can rotate freely so that the polymer is soft and elastic.
The thermal motion of the polymer chains controls the gas diffusion process.
The diffusion coefficients are independent of the gas concentration when the
penetrants are low-sorbing permanent gases [15]. However, strong derivation from
Henrys law expressed as non-linear sorption isotherms is observed when

27
condensable gases (e.g. CO2, hydrocarbons) are at sufficiently high pressure.
These phenomenon could be described by using the Flory-Huggins equation [16]:

= ( ) = + (1 ) + (1 ) 2 (2-13)

where is penetrant activity in the gas phase contiguous to the polymers, p and
ps are the partial pressure and saturation vapor pressures of the gas, respectively,
is the volume fraction of penetrant dissolved in the polymer, and is the
so-called FloryHuggins interaction parameter. In such condition, a linear or even
exponential increase in diffusivity coefficient is observed [17].
2.5 Gas Transport in Glassy Polymers
Most of the differences in transport behavior between glassy and rubbery
polymers stems from the non-equilibrium nature of glassy polymers. Glassy
polymers can be considered as a super-cooled liquid, thus excess free volume is
created due to the lack of sufficient relaxation time for polymer chains. The
diffusion coefficients strongly depend on the free volume of the polymer. From
another aspect, the thermal motion of glassy polymer is limited due to the steric
hindrance along the polymer backbone so that the gas diffusion coefficient is
normally lower than that of rubber.
28
2.6 Effect of Temperature
The temperature dependence of solubility, diffusivity and permeability
coefficients may be described by an appropriate combination of vant Hoff and
Arrhenius expressions, in the absence of any thermal transitions [18, 19].
S S 0 exp( H s / RT ) (2-14)
D D0 exp( Ed / RT ) (2-15)
P P0 exp( E P / RT ) (2-16)
where S0, D0 and P0 are the pre-exponential factors. Hs is the heat of sorption, Ed is
the activation energy for diffusion, and Ep is the apparent activation energy for
permeation. Because the sorption could be considered as the marriage of two
hypothetical thermodynamic steps, which are the condensation of the pure
penetrant and the mixing of the pure penetrant with the polymer matrix, the
apparent activation energy is rewritten as follows:
E p Ed H cond H mix
(2-17)
29
References
[1] D.R. Paul, O.M. Ebra-Lima, Pressure-Induced Diffusion of Organic Liquids
through Highly Swollen Polymer Membranes, Journal of Applied Polymer
Science, 14 (1970) 2201-2224.
[2] D.R. Paul, The Role of Membrane Pressure in Reverse Osmosis, Journal of
Applied Polymer Science, 16 (1972) 771-782.
[3] K. Ghosal and B. D. Freeman, Gas Separation Using Polymer Membranes: An
Overview, Polym. Adv. Technol., (1994) 24.
[4] R. R. Zolandz and G. K. Fleming, Membrane Handbook, in, Chapman & Hall,
New York, 1992.
[5] M.R. Coleman, W.J. Koros, Isomeric Polyimides Based on Fluorinated
Dianhydrides and Diamines for Gas Separation Applications, Journal of
[6] M. Salame, Prediction of Gas Barrier Properties of High Polymers, Polymer
Engineering & Science, 26 (1986) 1543-1546.
[7] J. Bicerano, Prediction of Polymer Properties, Marcel Dekker, 2002.
[8] W.M. Lee, Selection of Barrier Materials from Molecular Structure, Polymer
Engineering & Science, 20 (1980) 65-69.
[9] A.A. Bondi, Physical Properties of Molecular Crystals, Liquids, and Glasses,
Wiley, 1968.
30
[10] J.Y. Park, D.R. Paul, Correlation and Prediction of Gas Permeability in
Glassy Polymer Membrane Materials Via a Modified Free Volume Based
Group Contribution Method, Journal of Membrane Science, 125 (1997)
23-39.
[11] M.W. Hellums, W.J. Koros, G.R. Husk, D.R. Paul, Fluorinated
Polycarbonates for Gas Separation Applications, Journal of Membrane
Science, 46 (1989) 93-112.
[12] M.R. Pixton, D.R. Paul, Gas Transport Properties of Polyarylates: Substituent
Size and Symmetry Effects, Macromolecules, 28 (1995) 8277-8286.
[13] K.-S. Chang, C.-C. Tung, K.-S. Wang, K.-L. Tung, Free Volume Analysis and
Gas Transport Mechanisms of Aromatic Polyimide Membranes: A Molecular
Simulation Study, The Journal of Physical Chemistry B, 113 (2009)
9821-9830.
[14] E. Sada, H. Kumazawa, P. Xu, H. Nishikawa, Gas Transport in Rubbery
Polymers, Journal of Applied Polymer Science, 33 (1987) 3037-3044.
[15] A.Y. Alentiev, V.P. Shantarovich, T.C. Merkel, V.I. Bondar, B.D. Freeman, Y.P.
Yampolskii, Gas and Vapor Sorption, Permeation, and Diffusion in Glassy
Amorphous Teflon Af1600, Macromolecules, 35 (2002) 9513-9522.
[16] J.H. Petropoulos, Mechanisms and Theories for Sorption and Diffusion of
Gases in Polymers, in: D.R. Paul, Yampol'skii, Y. P. (Ed.) Polymeric Gas
Separation Membranes, CRC Press, Boca Raton, FL, 1994, pp. 17-81.
31
[17] H. Lin, B.D. Freeman, Gas and Vapor Solubility in Cross-Linked
Poly(Ethylene Glycol Diacrylate), Macromolecules, 38 (2005) 8394-8407.
[18] T.H. Kim, W.J. Koros, G.R. Husk, Temperature Effects on Gas Permselection
Properties in Hexafluoro Aromatic Polyimides, Journal of Membrane Science,
46 (1989) 43-56.
[19] W.J. Koros, W.C. Madden, Transport Properties, John Wiley & Sons, Inc.,
2002.
32
CHAPTER 3 Materials and Experimental Methods
3.1 Materials
Extem XH 1015 was obtained from SABIC Innovative Plastics (formerly GE
Plastics) and was dried at 120 C overnight in a vacuum oven before use. It is
synthesized from bisphenol-A dianhydride (BPADA) and diamino diphenyl sulfone
(DDS) via condensation polymerization as shown in Figure 3-1.
Figure 3-1 Synthetic route of Extem XH1015
The glass-transition temperature of Extem 1015 was determined at a heating
rate of 10 C/min by a PerkinElmer DSC6000, defined as the midpoint of change in
heat capacity during the second heating. Matrimid 5218, a thermoplastic polyimide
made from the monomers 3,3,4,4-benzophenone tetracarboxylicdianhydride
(BTDA) and diaminophenylindane (DAPI), was used as received from Huntsman
Advanced Materials. Polysulfone made from bisphenol A was also used. Their
chemical structures are summarized in Table 3-1. Some bulk properties of these
polymers (i.e., gas permeability, density, etc.) are given in Table 3-2.
33
Table 3-1 Chemical structures of polymer used in this study
Polymer name Structure
O O
Polyetherimide, O
N N S
n
O O O
Extem 1015 O O
O O O
Polyimide,
N N
Matrimid 5218 n
O O
O
Polysulfone, PSF
O S O
n
O
Table 3-2 Bulk properties of polymers used in this study
Polymer Density, Glass-transition Permeability, P (barrera) Selectivity
(g/cm3) temperature, (C) O2 N2 CH4 CO2 O2/N2
Polyetherimide, Extem [1]. 1.31 260 (267b) 0.81 0.13 0.13 3.3 6.2
Polyimide, Matrimid [2] 1.20 310 1.7 0.25 0.19 6.5 6.8
Polysulfone, PSF [3] 1.24 186 1.4 0.25 0.25 5.6 5.6
a
1 barrer = 1 10-10 cm3 (STP) cm cm-2 s-1 cm-Hg-1
b
Glass-transition temperature provided by supplier [1].
JeffamineED-2003 (O,O-Bis(2-aminopropyl) polypropylene
glycol-block-polyethylene glycol-block-polypropylene glycol, Mw: 2000g/mol),
ethanol (AR grade), 3-glycidyloxypropyltrimethoxysilane (GOTMS) were
purchased from Sigma-Aldrich and used as received. Polyethylene glycol (400,
34
1000, 1500 and 2000g/mol) were purchased from Sigma-Aldrich.
Methoxy-PEG-azide (Mw: 350 and 1100g/mol.) were obtained from Creative
PEGWorks and used without further treatment. Concentrated hydrochloric acid
from Fisher Scientific was employed as the catalyst for the hydrolysis of GOTMS.
Cyclohexanone, the solvent, was purchased from Fisher Scientific and dried
with molecular sieves before use. Dicholoromethane (DCM) was purchased from
Merck and utilized without further purification.
The gases, N2, O2, CH4 and CO2 were provided by Matheson Tri-gas and were
at least 99.99% pure. High purity compressed H2 (99.999%) and CO2/N2 (50:50)
mixed gases were purchased from SOXAL, Singapore.
3.2 Preparation of Dense Membranes
3.2.1 Preparation of Glassy Thick Membranes
Dense Extem membranes were fabricated using a solution casting method
described elsewhere26. In short, a solution was prepared by dissolving 2 wt% of the
polymer sample in a solvent of DCM. The solution was then filtered through a 1m
filter (Whatman) and cast onto a Si wafer with a metal ring on top. The whole plate
was leveled horizontally and covered with a glass plate. A small gap was left to
35
allow slow solvent evaporation to form a dense membrane. The nascent membrane
was further dried at 250C under vacuum for 48h to remove residual solvents.
3.2.2 Preparation of Organic-Inorganic Membranes (OIMs)
The synthetic route as shown in Figure 3-2 is similar to the report by Shao and
Chung [4]. The molar ratio of GOTMS, ethanol, water and hydrochloric acid in the
hydrolysis solution was 1:1.13:3.2:0.05. After stirring for 60 min at room
temperature, the alkoxysilane solution was transferred to the mixed solvent of
water/ethanol (30/70 wt%) containing 2 wt% of Jaffamine ED-2003. The molar
ratio of GOTMS to Jaffamine ED-2003 was kept at 4:1 in all samples. The
solution was then heated to 60 C and while stirring for 1 hour to facilitate the
epoxy-amine reaction and preliminary condensation. Afterwards, the
predetermined amount of PEG was added into the mixture and stirred for 10
minutes, followed by filtration through a 5m Waterman filter. The solution was
poured into a homemade Teflon petri dish which was placed level in an oven at 30
C. The Teflon dish was covered with an aluminum foil with small holes to control
the evaporation rate of solvent. After drying at 30 C for 1 day, the oven temperature
was increased to 40 C for 2 days. Subsequently, the membranes were moved into a
vacuum oven at 70 C for 1 day to complete the condensation reaction and remove
the residual solvents. The membranes were sealed into a zip-lock bag and put into a
refrigerator (-20 C) for 2 hours to induce crystallization of the free PEGs which
36
were dispersed in the GOTMS-Jaffamine matrix. At the end, the membrane samples
were peeled off the petri dish and stored in a desiccator for testing and
characterization. The thermal history of these samples was kept the same for easy
comparison of various properties.
Figure 3-2 Synthetic route of hybrid membranes
The molar ratio of GOTMS to Jaffamine ED-2003 was maintained at 4:1 for
all the matrices. The gas permeation performance of the hybrid membranes in
other ratios could be found in a previous work [4]. Four PEGs (all with two
hydroxyl end groups) of different molecular weights were blended into the
GOTMS-PEO (also referred as GP w/o PEG) matrices. The blended hybrid

37
membranes are represented by GPPX-Y-Z, in which GPP represents the
GOTMS-PEO-PEG blend, X represents the molecular weight of blended PEG, Y
represents the weight percentage of the blended PEG, and Z represents the
temperature. For example, GPP1000-40-35 means the matrix contains 40 wt% of
free PEG1000 tested at 35 C.
For hybrid membranes with Methoxy-PEG-azide, the preparation procedure is
similar. Methoxy-PEG-azide was used to replace PEG in the physical blending
step. Figure 3-3 shows the scheme of membrane synthesis involving
Methoxy-PEG-azide.
Figure 3-3 Synthetic route of OIMs containing PEG-azide and the

subsequent thermal reactions
38
In the last step, these OIMs blended with PEG-azide were peeled off and
stored in a desiccator before any characterization. Thermal grafting was
performed in a vacuum furnace by ramping the temperature from ambient to 140
C at 1 C/min and holding for 12 hours. The thickness of the obtained membranes
ranged from 150 m to 300 m. The blended hybrid OIMs are labeled by
GPAX-Y, in which GPA represents the GOTMS-PEO PEG-azide blend, X
represents the molecular weight of blended PEG, and Y represents the weight
percentage of the blended PEG. For example, GPA1100-20 means the OIM
contains 20 wt% of PEG-azide 1100g/mol.
3.3 Preparation of Polymeric Thin Films
Thin films of Extem were made by spin-coating polymer solutions onto
silicon wafers. The solution was prepared by dissolving dried Extem in
cyclohexanone at 80 C and slowly cooling to room temperature. The solution
was filtered through 0.45m, 0.2m and 0.1m Whatman PTFE membranes to
eliminate any particles that could create pinholes in the thin films. Film thickness
was controlled by adjusting the solution concentration from 3 wt% to 5 wt% and
the spin speed from 1000 to 1400 rpm. For different polymers, these parameters
vary due to different solution viscosity and volatility. A layer of highly permeable
poly(dimethylsiloxane) (PDMS) was spin-coated on top of the Extem thin films in
order to block possible pin holes and provide extra ease of handling. According to
39
the series resistance model [5], the permeability of the composite membrane is
given by the following equation,

composite
= PDMS + Extem (3-1)
composite PDMS Extem
where lcomposite, lPDMS and lExtem are the thickness of the composite membrane, the
PDMS and the Extem layers, respectively; Pcomposite, PPDMS and PExtem are the
permeability coefficients of the composite membrane, the PDMS and the Extem
layers. The PDMS coating layer is approximately 3m thick and the typical CO2
permeability is 3800 barrer [6], while the Extem layer is 160 nm thick and the
CO2 permeability is only 3 barrer. The contribution of the PDMS layer to the total
resistance is less than 2% so that it has negligible effect on the measured
permeation rate. On the other hand, the PDMS layer does not undergo physical
aging itself and appears to have little or no influence on the behavior of the
underlying glassy layer as reported by Rowe et al. [7]. In short, the effect of the
PDMS layer on the physical aging and CO2 plasticization behavior of the Extem
films can be ignored. The wafer with the two polymer layers was then placed on a
hot plate at 110 C for 15 min to crosslink the PDMS and removal all the residual
solvent. More details about the PDMS coating technique can be found elsewhere
[8]. The bi-layer film was lifted from the wafer by using water and mounted on a
square copper wire frames [9]. Samples were dried in an oven at 100 C overnight
to remove the residual water and solvent.
40
All the samples were heated above the bulk Tg of Extem for 15 min in a N2
atmosphere and then rapidly quenched to room temperature immediately. This
process erases the prior thermal history of the glassy polymer layer and relaxes any
chain orientation imparted during spin-coating. The point at which the film is
quenched is defined as the zero time in the aging experiment. Previous work has
shown that prior history of a thin film can have an important effect on its aging
behavior [10]. On the other hand, care has to be taken to avoid polymer degradation
while annealing above Tg. Extem is a relatively new commercial polymer , and
published information about this material is quite limited [11, 12]. In this work, the
Extem films were annealed at 282 C to ensure completed removal of prior thermal
history.
3.4 Characterization of Physicochemical Properties
3.4.1 Measurement of Gel Content
To examine the extent of polycondensation in the sol-gel system, the nascent
membranes were subjected to water immersion for 1 week. The remaining
insoluble samples were dried in the vacuum at 70 C for 24 hours to remove water
before weighing again. The gel content was calculated by equation 3-2.
% gel content = m/m0 100% (3-2)
where m and m0 are the weights of the insoluble fraction and the original weight
41
of the membrane, respectively.
3.4.2 Fourier Transform Infrared Spectrometer (FTIR)
The FTIR-ATR measurements were performed using a Perkin-Elmer FT-IR
Spectrometer Spectrum 2000 with scan range from 4000 cm-1 to 600 cm-1. The
Extem thin film used in FTIR-ATR was made by ring casting.
3.4.3 Transmission Electron Microscopy (TEM)
Ultra-thin films for a combined scanning transmission electron microscope
(STEM/EDX) were prepared by a solution method following the procedure used
for membrane casting.
3.4.4 Thermogravimetric Analysis (TGA)
The weight loss of OIMs containing Methoxyl-PEG-azide during thermal
treatment was characterized by thermogravimetric analysis (TGA) with a TGA
2050 Themogravimetric Analyzer (TA Instruments). The analysis was carried out
with a ramp of 10 C/min in the temperature range from 50 to 800 C. The purge
gas was N2 and its flow rate was controlled at 50 ml/min.
42
3.4.5 Wide Angle X-ray Diffraction (WAXD)
A wide-angle X-ray diffractometer (Bruker D8) was utilized to determine the
structures of the membranes at room temperature (25 C). Ni-filtered Cu K
radiation with a wave length of 1.54 was used in the XRD experiments. The
d-spacing was calculated based on the Braggs law n = 2dsin, where n is the
integral number, is the wavelength, d is the dimension spacing and 2 is the
diffraction angle.
3.4.6 X-ray Photoelectron Spectrometer (XPS)
The nitrogen 1s bonding energy change after thermal grafting was monitored
by an XPS spectrometer (Kratos Analytical Ltd., England) under ultrahigh
vacuum. All spectra were obtained at a photoelectron take-off angle vertical to the
sample.
3.4.7 Elemental Analysis
The elemental analysis was carried out using a Flash EA 1112 Elemental
Analyzer manufactured by Thermo Electron. The analyzer was able to determine
CHNS (Carbon, hydrogen, nitrogen and sulfur) on dried samples. The oxygen
content was obtained by the subtracting the ash % plus the total for carbon,
43
hydrogen, nitrogen and sulfur.
3.4.8 Nuclear Magnetic Resonance (NMR)
NMR analyses were conducted using a Bruker 400 FT-NMR spectrometer at a
resonance frequency of 400.132 MHz for 1H and 100.621MHz for 13

C, while 1H
NMR spectra (1D, homonuclear decoupling) were obtained from an Extem XH
1015 pellet sample dissolved in DMSO-d6 using a 5 mm BBO (broadband observe)
probe. Other spectra were performed in CDCl3 and chemical shifts are given in ppm
unit.
The chemical structure changes of OIMs with PEG-azide after thermal grafting
were characterized by solid state 13C NMR (100.6 MHz) with magic angle spinning
(MAS) at 7.5 kHz performed on a Bruker DRX 400 spectrometer.
3.4.9 Simulation Based on Molecular Dynamics
Molecular dynamic simulations were conducted using Material Studio 4.4
from Accelrys. Polymer chains consisting of 10 repeat units of polysulfone (PSU),
Ultem or Extem were constructed via a polymer build function, followed by
energy minimization separately. Initiator and terminator were unknown because of
44
limited publications or information on these commercial polymers. The isotactic
configuration with random torsion and head-to-tail orientation was assumed prior
to the amorphous cell construction. Besides, polymer chains consisting of 5 repeat
units were also constructed in order to discuss the chain packing morphology. Two
polymer chains of PSU, Extem and Ultem were put together and minimized in
order to discuss structural effects on chain packing. The initial density of the
polymer periodic cell was set as 0.1 g/cm3 in order to eliminate aromatic ring
catenation and chain scission during amorphous cell construction as suggested by
Heuchel and Hofmann [13]. Four polymer chains were employed for amorphous
cell construction based on compass force field calculations by Amorphous Cell
module. Conformational optimization and fine convergence with a maximum
iteration of 10,000 was performed before molecular dynamics simulations to
proceed. The detailed information for cell models built is listed in Table 3-3. The
equilibrium stage temperature was set to 308 K when MD (molecular dynamics)
by Discover module was launched. This is because all the pure gas permeability
data were collected at 35C. A set of MD under isothermal-isobaric (NPT) mode
were performed to compress amorphous cell density from 0.1 g/cm3 to the
experimental density. The simulated densities are listed in Table 3-2. The total MD
time for each polymer was 500 ps in order to allow the amorphous cell to reach
equilibrium.
45
Table 3-3 Atom numbers and cell dimensions for PSU, Extem and Ultem
amorphous cells
The fractional accessible volume (FAV) was calculated from the free volume
and occupied volume simulated by the Connolly task. The FAV distribution of
each polymer was plotted by using different diameter probes to detect available
volume in the amorphous cell. For one particular diameter there is one unique FAV,
which means only particles smaller than the probe could go through or occupy the
volume under this definition. Thus, this so called Connolly task corresponds to the
kinetic diameters of gases employed. In this study, we choose probe diameters
ranging from 2.0 to 5.0 , not only because even the diameter of smallest
helium molecules is bigger than 2.0 , but also the number of cavities larger than
5.0 is very small and can be ignored, compared to that of the smaller cavities.
3.4.10 Variable Angle Spectroscopic Ellipsometer
A variable angle spectroscopic ellipometer (J.A. Woollam Co., model 2000D)
was used to characterize the thickness of thin films on a silicon substrate.
Simultaneous measurement of more than 500 wavelengths ranged from 193 to
46
1000 nm could be achieved by using two different types of lamps (deuterium lamp
and quartz tungsten halogen lamp). A three-layer model consisting of Si, SiO2 and
Cauchy layer was used to fit the thickness of thin polymeric films. The Cauchy
model as follows is valid since the film was transparent over the measured
spectral range:

() = + 2 + 4 (3-3)
where n is the refractive index, is the wavelength of the sodium (Na) D under
room temperature, A, B and C are constants obtained from the regression analysis.
3.5 Characterization of Gas Transport Properties
3.5.1 Pure Gas Permeation Tests
A constant volume method was employed to obtain the pure gas permeability
[14] and the solution-diffusion mechanism was used to explain the gas transport
properties through dense membranes [15]. The measured rate of pressure increase
(dp/dt) at steady state was used to calculate the gas permeability according to the
following equation.
273.15 1010 Vl dp
P
760 AT ( p 76 / 14.7) dt
(3-4)
where P is the gas permeability in barrer (1 barrer = 11010 cm3 (STP) cm/cm2
s cmHg), V is the volume of downstream chamber (cm3), l is the membrane
47
thickness (cm), A is the effective area of membrane (cm2), T is the operating
temperature (K) and p is the upstream operating pressure (psia).
3.5.2 Mixed Gas Permeation Tests
The mixed gas permeation properties for these hybrid membranes were
obtained with a lab-made mixed gas permeation cell as described in the work of
Xia et al. [16]. OIMs samples were tested with a CO2/N2 (50%/50% mole fraction)
binary gas and anlysised by gas chromatography at 45 C with a total pressure of 4
atm. The gas permeability of CO2 and N2 is calculated by following equations:
273.15 1010 yCO2Vl dp

PCO2
760 AT (76 / 14.7)( xCO2 p) dt
(3-5)
273.15 1010 (1 yCO2 )Vl dp

PN2
760 AT (76 / 14.7)[(1 xCO2 ) p] dt
(3-6)
where yCO2 is the mole fraction of CO2 in the feed gas, and xCO2 is the mole
fraction of CO2 in the permeate.
3.5.3 Pure Gas Sorption Tests
Sorption measurements from 30 C to 50 C were conducted by using the
gravimetric sorption technique (Cahn D200 microbalance sorption cell) which
could be found elsewhere [17]. The sorption cell loaded with approximately 70
48
mg samples was evacuated overnight prior to sorption testing. From the weight
gain, the amount of gas absorbed could be obtained after buoyancy correction.
Therefore, the solubility coefficient could be obtained by fitting the slope of the
sorption isotherms. The diffusivity of gas penetrants was then calculated from
solubility and permeability.
49
References
[1] S. Lee, Extreme Performance - or Processability?: New Tp Polyimide Offers
Both, in: Plastics Technology, January 2007.
[2] P.S. Tin, T.S. Chung, Y. Liu, R. Wang, S.L. Liu, K.P. Pramoda, Effects of
Cross-Linking Modification on Gas Separation Performance of Matrimid
Membranes, Journal of Membrane Science, 225 (2003) 77-90.
[3] J.S. McHattie, W.J. Koros, D.R. Paul, Gas Transport Properties of
Polysulphones: 1. Role of Symmetry of Methyl Group Placement on
Bisphenol Rings, Polymer, 32 (1991) 840-850.
[4] L. Shao, T.S. Chung, In Situ Fabrication of Cross-Linked Peo/Silica
Reverse-Selective Membranes for Hydrogen Purification, International
Journal of Hydrogen Energy, 34 (2009) 6492-6504.
[5] J.J. Shieh, T.S. Chung, D.R. Paul, Study on Multi-Layer Composite Hollow
Fiber Membranes for Gas Separation, Chemical Engineering Science, 54
(1999) 675-684.
[6] T.C. Merkel, V.I. Bondar, K. Nagai, B.D. Freeman, I. Pinnau, Gas Sorption,
Diffusion, and Permeation in Poly(dimethylsiloxane), Journal of Polymer
Science Part B-Polymer Physics, 38 (2000) 415-434.
[7] B.W. Rowe, B.D. Freeman, D.R. Paul, Physical Aging of Ultrathin Glassy
Polymer Films Tracked by Gas Permeability, Polymer, 50 (2009) 5565-5575.
50
[8] N.R. Horn, D.R. Paul, Carbon Dioxide Plasticization of Thin Glassy Polymer
Films, Polymer, 52 (2011) 5587-5594.
[9] Y. Huang, D.R. Paul, Experimental Methods for Tracking Physical Aging of
Thin Glassy Polymer Films by Gas Permeation, Journal of Membrane
Science, 244 (2004) 167-178.
[10] B.W. Rowe, B.D. Freeman, D.R. Paul, Influence of Previous History on
Physical Aging in Thin Glassy Polymer Films as Gas Separation Membranes,
Polymer, 51 (2010) 3784-3792.
[11] N. Peng, T.S. Chung, M.L. Chng, W. Aw, Evolution of Ultra-Thin
Dense-Selective Layer from Single-Layer to Dual-Layer Hollow Fibers Using
Novel Extem (R) Polyetherimide for Gas Separation, Journal of Membrane
Science, 360 (2010) 48-57.
[12] J. Xia, S. Liu, P.K. Pallathadka, M.L. Chng, T.S. Chung, Structural
Determination of Extem XH 1015 and Its Gas Permeability Comparison with
Polysulfone and Ultem Via Molecular Simulation, Industrial & Engineering
Chemistry Research, 49 (2010) 12014-12021.
[13] M. Heuchel, D. Hofmann, Molecular Modelling of Polyimide Membranes for
Gas Separation, Desalination, 144 (2002) 67-72.
[14] W.H. Lin, R.H. Vora, T.S. Chung, The Gas Transport Properties of
6FDA-Durene/1,4 Phenylenediamine (PPDA) Copolyimides, J. Polym. Sci.
Polym. Phys., 38 (2000) 2703-2713.

51
[15] W.J. Koros, W.C. Madden, Transport Properties, John Wiley & Sons, Inc.,
2002.
[16] J. Xia, S. Liu, C.H. Lau, T.S. Chung, Liquid-Like Polyethylene Glycol
Supported in the Organic-Inorganic Matrix for CO2 Removal,
Macromolecules, 44 (2011) 5268-5280.
[17] T.S. Chung, S.S. Chan, R. Wang, Z. Lu, C. He, Characterization of
Permeability and Sorption in Matrimid/C60 Mixed Matrix Membranes,
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52
CHAPTER 4 Liquid-like Polyethylene Glycol Supported
in the Organic-inorganic Matrix for CO2 Removal
This chapter was published as a journal paper:
J. Xia, S. Liu, C.H. Lau, T.S. Chung, Liquid-like polyethylene glycol supported in
the organic-inorganic matrix for CO2 removal, Macromolecules, 44 (2011)
5268-5280
53
Abstract
This chapter introduces a novel method to improve CO2 permeability and
CO2/light gas permselectivity by adding polyethylene glycol (PEG) into the
PEG-silica organic-inorganic hybrid matrix. The matrix is cross-linked by in situ
formation of silica nano particles with diameters ranging from 1 to 5 nm. These
particles disperse homogenously in the organic phase according to the morphology
studied by scanning TEM. Many small particles were evolved after blending PEG
into the matrix due to a high fraction of bi-functional and tri-functional silicon
containing groups. Four PEGs with different molecular weights (Mw = 400, 1000,
1500, 2000g/mol) are added into the matrix prior to the matrix formation.
Permeability coefficients of three pure gases (H2, N2 and CO2) and one mixed gas
(CO2/N2) are measured to explore the effects of PEG content and molecular weight
on the gas transport properties. The membrane containing 60 wt% of 1000 g/mol
PEG achieved an ultra-high CO2 permeability of 845 Barrer with CO2/H2 and
CO2/N2 permselectivity around 10 and 40, respectively. Fundamental studies on the
effect of temperature on gas diffusivity and solubility are also carried out.
Molecular weights of PEGs have been proved to play a crucial role in determining
the permeability and diffusivity.
54
4.1 Introduction
The failure of the 2010 United Nations Climate Change Conference in Cancun
clearly indicated the increasing difficulty in forcing governments around the world
to control carbon dioxide emission [1]. In this context, clean energy technology
emerges as an important solution to overcome the dilemma between the economic
development and the fight against global warming [2]. Reports show that more than
30% of CO2 produced by human activities are attributed to the running of coal-fired
power stations [3]. In this sense, the capture of CO2 in the coal-fired power
generation industry is especially significant in worldwide CO2 control. Meanwhile,
compared with other small individual sources of CO2 generation, large and
centralized coal-fired power stations provide more convenience in the monitoring
and control of CO2 emission. Therefore, the technology of CO2 removal from large
coal-fired power plants is highly demanded.
The IGCC (Integrated Gasification Combined Cycle) power plant program,
which is the core technology of FutureGen sponsored by the U.S. Department of
Energy, requires extensive applications of high efficient CO2 removal technology
[4]. Currently there are three major approaches to reduce CO2 emission:
pre-combustion capture, oxyfuel combustion and post-combustion capture [5].
55
Several technologies have already been developed for CO2 separation from light
gases, including amine adsorption [6], pressure-swing adsorption [7] and
membrane separation [4, 8-18]. Each technology has its own pros and cons.
Membrane separation systems may have drawbacks at the current stage, such as
relatively lower permselectivity for CO2 over light gases and additional
recompression cost compared to amine based adsorption systems; however,
membrane based CO2 capture business appears to be more promising because new
materials with ultra-high CO2 permeability or permeance have been continuously
developed [5].
In H2-selective glassy membranes, H2 gas molecules are smaller and thus diffuse
faster than CO2 [19-21]. Usually, H2-selective membranes are made of glassy
polymers, which have better thermal stability and mechanical property than rubbery
polymers [22]. However, most H2-selective membranes have a trade-off relation
between gas permeability and permselectivity, which leads them more inferior to
rubbery membranes for CO2 removal [23]. Reverse-selective membranes made
from rubbery materials, like silicon rubber [24, 25] and polyethylene oxide (PEO)
[15, 26-36], could be promising materials for CO2 removal, because larger CO2
molecules, due to higher solubility, can pass through these membranes faster than
H2 and N2. In recent years, many PEO or polyethylene glycol (PEG) based CO2
reversible selective membranes have been developed because of their high ethylene
56
oxygen concentrations, including PEO copolymers [16, 30, 37], PEO blends [8, 9,
30, 33, 34, 37-40] and cross-linked PEO [11, 15, 33, 41-44]. However, PEO is easy
to crystallize, resulting in reduced free volume and lower permeability [28].
Many approaches have been reported to reduce the crystallization tendency of
PEO/PEG. They may be briefly summarized as follows based on their own unique
systems.
a) PEO copolymer: The crystallization of ethylene oxide (EO) segments can be
prevented if the EO segments are too short to line up with the neighboring EO
chains [39].
b) Cross-linked PEO: Lin et al. [15, 26] have developed a series of membranes
with CO2 permeability of 400 Barrer at 35 C by cross-linking poly (ethylene
glycol diacrylate). Shao and Chung [10] have synthesized a series of
cross-linked organic-inorganic membranes by in situ formation of nano silica
particles. The CO2 permeability of these membranes reached 300 to 492 Barrer
with ideal permselectivity of 8-9.
c) PEO Blends: Liquid PEG (Mw = 300 g/mol) was directly impregnated into the
microporous region of a cellulose membrane by Kawakami et al. [40].
Surprisingly, the CO2 permeability was only 82 Barrer at 25 C due to the
microporous tortuosity and the less permeable cellulose substrate. In order to
further improve the CO2 permeability and permselectivity, Car et al. [34, 37, 38]
57
and Yave et al. [8, 9, 30] have incorporated liquid PEG into thermoplastic poly
(amide-b-ethylene oxide) and poly (ethylene oxide)-poly (butylenes
terephthalate) multi-block copolymers via physical blending. However, the high
percentage of hard amide segments in these copolymers still has a negative
effect on permeability enhancement.
Ideally, liquid PEG should be the best selective medium for CO2 removal
because of its high solubility and diffusivity, as well as the high permselectivity of
CO2/light gas. However, liquid PEG itself cannot form a free standing membrane.
Thus, a proper selection of matrix materials for hosting PEG is the key factor to
effectively use its superior gas separation properties towards the separation of
CO2/light gas.
In this chapter, organic-inorganic membranes (OIMs) developed in our
laboratory [10] are employed as the matrix to support the liquid PEG. In situ formed
silica nano particles connect the poly (propylene oxide)-b-poly (ethylene
oxide)-b-poly (propylene oxide) (PPO-PEO-PPO) chains, thus forming a dense
membrane with sufficient mechanical strength. Low molecular weight PEGs (Mw
= 400, 1000, 1500 and 2000 g/mol) are directly blended in the matrix as shown in
Figure 4-1. This technique has a few advantages: (1) high capacity to host free
PEGs (up to 60 wt%); (2) a similar structure between the matrix and the free PEGs;
58
(3) permeability could be tailored by changing the content or the molecular weight
of the PEGs. CO2 permeability ranging from 55.6 to 1040 Barrer is achieved by
using different PEGs at temperatures from 35 C to 55 C. CO2/H2 and CO2/N2
permselectivity varies from 6.0 to 10.7 and 26.2 to 52.4, respectively. The effect of
temperature is so significant that the permeability will increase 15 times with a
temperature increment of 25 C. The elimination of PEG crystals is the major
reason for the permeability jump. CO2 sorption study reveals that CO2 solubility
increases when the PEG melts. Among all these PEGs, PEG1000 is found to be the
best candidate to maximize both permeability and permselectivity. Interestingly,
CO2 diffuses faster if the molecular weight of PEGs is comparable to the PEO
segments in the matrix.
Figure 4-1 Concept of liquid PEGs supported in the organic-inorganic matrix
59
4.2 Results and Discussion
4.2.1 Basic Physicochemical Properties
All the membrane samples show crosslinked characteristics in gel content
experiments as summarized in Table 4-1. For the GP w/o PEG sample, 96% of the
reactants are cross-linked. For other samples with blended PEGs, the
organic-inorganic matrices are insoluble while the blended PEGs can be
completely washed out. On the whole, the organic-inorganic matrix is successfully
fabricated regardless of the PEG loading.
Table 4-1 Gel content (%) of GP w/o PEG and GPP series
GP w/o PEG 961
20 wt (%) 40 wt (%) 60 wt (%)
GPP400 751 532 362
GPP1000 761 561 341
GPP1500 771 552 332
GPP2000 771 581 362
The GP w/o PEG and GPP400 membranes are transparent because their melting
points are below room temperature as shown in Table 4-2, while GPP1000,
GPP1500 and GPP2000 are translucent due to the existence of PEG crystals.
60
Transparency of GPP400 series indicates that the silica nano particles are
dispersed homogeneously.
Good dispersion of silica nano particles in the matrix is also observed in the
STEM graphs given in Figure 4-2a and 4-2b. The EDX spectrum in Figure 4-2c
reveals that these nano-particles are composed of silica. The regular shape and
sharp edges of nano particles in Figure 4-2a shows that these particles are in the
crystal form. The distance between two particles varies from 5 nm to 50 nm, most
of which are larger than the fully extended PPO-PEO-PPO polymer chain
(approximately 10 nm estimated from the bond length). Thus, incomplete
cross-linking may exist.
61
Table 4-2 Thermal properties of GPP series, GP w/o PEG and pure PEGs
Tm2o Tm2p Tc2o Tc2p -Hc -Hc

a b c d e
(C) (C) (C) (C) (J/g) (J/g)f
GP w/o PEG 14.9 24.5 -20.1 -24.5 51 N/A
Jaffamine
29.4 37.2 15.6 11.2 114 N/A
ED-2003
GPP400-20 9.7 20.5 -6.8 -13.8 58 66
GPP400-40 7.2 19.3 -7.7 -14.3 77 80
GPP400-60 6.4 20.0 -5.7 -13.3 88 95
PEG400 -9.5 7.7 -15.1 -21.2 123 N/A
GPP1000-20 -8.1 35.2 12.5 4.5 74 73
GPP1000-40 16 41.7 20.8 14.2 92 94
GPP1000-60 21.6 45.0 24.9 15.7 120 116
PEG1000 32.3 40.7 26.7 22.3 159 N/A
GPP1500-20 32.3 43.3 10.9 1.5 75 73
GPP1500-40 42.2 46.8 22.9 17.3 87 94
GPP1500-60 42.3 48.5 26.7 23.5 115 115
PEG1500 37.7 47.0 24.0 19.5 158 N/A
GPP2000-20 35.8 46.2 15.9 7.2 70 76
GPP2000-40 47.2 52.3 29.3 26.0 102 101
GPP2000-60 51.7 54.7 32.8 28.0 123 125
PEG2000 48.2 56.2 34.3 29.7 175 N/A

a
Onset melting temperature of the 2nd heating curve
b
Peak melting temperature of the 2nd heating curve
c
Onset crystallization temperature of the 2nd cooling curve
d
Peak crystallization temperature of the 2nd cooling curve
e
Hc is the heat of crystallization obtained experimentally from DSC
f
Hc is the theoretical value calculated by equation 4-1
62
In this sol-gel system, any intermediates species, like [-Si-(OH)2OCH3] or
[-Si-(OCH3)2OH] would be considered as the result of partial hydrolysis and
condensation. In addition, two partially hydrolyzed species may link together to
form a siloxane [Si-O-Si] bond as illustrated by structure B in Figure 4-3c. In
other words, not all the silicon portion of the precursors will participate in the
construction of silica nanoparticles. Instead, some of them may only contribute
one silicon-containing group while the rest remains flexible. The white dashed
lines in Figure 4-3a are drawn for the illustration of possible network topology. In
Figure 4-3b, the white solid lines schematically represent the possible polymer
alignment. Four kinds of groups with different degrees of hydrolysis (i.e., A, B, C
& D in the bottom of Figure 4-3c) play different roles in constructing the network.
The un-hydrolyzed groups (A) prevent the precursor from crosslinking and
functions as the end groups as illustrated in Figure 4-3b. The mono-functional
groups (B) bridge two crosslinking precursors and extending the polymer chain
length between two nano-particles. Bi-functional (C) and Tri-functional (D)
groups may crosslink together and form the silica nano particles. The silicon
signal of un-hydrolyzed (A) and mono-functional (B) groups cannot be observed
by STEM due to the resolution limitation.
Above hypotheses are supported by the analyses done by ImageJ [45] as shown
63
in Figure 4-4a and Table 4-3. In the image analyses, black and white are inversed
for better particles identification. The average particle size (nm2) and the total area
fraction are calculated by using different STEM pictures to achieve statistical
results. Based on the 2-D area fraction information, relatively less silica content is
observed in GP w/o PEG in Figure 4-4a than that in GPP1500-60 in Figure 4-4b
by comparing with their theoretical weight percentages, although we cannot
calculate the volume fraction from the area fraction directly. The missing
silicon-containing components in GP w/o PEG are assigned to un-hydrolyzed and
mono-functional groups (i.e., A & B in Figure 4-3c), which are too small to be
captured by STEM. Conversely, a considerable portion of much smaller silica
particles in GPP1500-60 can be observed in Figure 4-2b and 4-4b, although fewer
bigger silica particles exist. These tiny nano dots (3.0 nm2) are located around the
agglomerated patterns, and all the particles in GPP1500-60 do not exhibit a
regular sharp edge as observed in GP w/o PEG. The distance from one dot to
another is less than 5 nm, which is in the length range of PPO-PEO-PPO segments
of the matrix. These are the strong evidences to prove that the cross-linking in
GPP1500-60 involves more structure C and D rather than structure A and B in
Figure 4-3c.
The hydrophilic PEGs absorb the water released from the condensation
reactions. Thus, the reaction equilibrium moves to the product side. In other words,
64
more silica nano particles will be formed instead of being individual silicon
containing functional groups. This is also consistent with the result of particle area
analyses in Table 4-3. Strong affinity of PEG with water molecules promotes the
condensation reaction and the formation of nano-silica nuclei. Another reason of
the morphological difference is that the high viscosity of PEG molecules prevents
the growth of nano silica nuclei from forming bigger particles.
Figure 4-2 STEM images of (a) GPP without free PEG and (b) GPP1500-60 and
(c) EDX analysis of silica particles
65
Figure 4-3 STEM images of (a) hybrid membranes and (b) imaginary matrix
constructed with (c) different functional groups
Figure 4-4 STEM images of hybrid membranes after imageJ analysis: (a) GPP
w/o PEG and (b) GPP1500-60
66
Table 4-3 Average size and area fraction of silica particles in GP w/o PEG and
GPP1500-60
Count Average Area Silica wt.

size (nm2) Fraction (%) (%)
GP w/o PEG 1064 442 7.52 11.1

GPP1500-60 137070 3.00.2 4.71 4.4
4.2.2 XRD Characterization
The smooth broad peak in Figure 4-5a shows that GP w/o PEG is amorphous at
room temperature because freezing at -20C cannot induce crystallization as its Tc
is -24.4C. GPP400 series are also amorphous because their melting points are
below room temperature. GPP1000, GPP1500 and GPP2000 series show two
characteristic peaks of PEO in Figure 4-5b, c and d. The peak at scattering angle 2
= 19.2 (d=4.62) corresponds to the reflections from (120) planes of the
monoclinic PEG crystal. Another peak at 2 = 23.3 (d=3.81) contains the
overlapped reflections from (032), ( 132 ), (112), ( 212 ), ( 124 ), ( 204 ), and (004)
planes [46].
67
Figure 4-5 XRD patterns for (a) GPP400, (b) GPP1000, (c) GPP1500 and (d)
GPP2000 at room temperature
4.2.3 The Gas Permeation Performance
CO2 permeability and CO2/light gas permselectivity of PEO based membranes
strongly depends on the EO group concentration [23]. Due to the existence of PEG
crystals, which are thought to be impermeable, CO2 permeability and CO2/light gas
permselectivity are compromised. By rising the temperature, CO2 permeability and
CO2/light gas permselectivity could ramp up because of more available EO groups
after melting. In this matrix, the molecular weight of PEGs also plays a key role in
determining the performance for the reason of interactions at molecular level.
Above factors will be described in more detail in the following sections. The best
68
data point with CO2 permeability of 696 barrer and CO2/H2 selectivity at 10.6 at
35C almost reaches the empirical limit compared to the upper bound [47], as
shown in Figure 4-6a, while the CO2/N2 separation performance already exceeds
the upper bound [26] as shown in Figure 4-6b.
Figure 4-6 Selected permeability/selectivity data map for (a) CO2/H2 and (b)
CO2/N2 separation at 35C
The CO2, H2 and N2 permeability of GPP400, 1000, 1500 and 2000 series at
different temperatures are depicted in Table 4-4. For easy comparison, gas
permeation performance of GP w/o PEG and pure semi-crystalline PEO are also
listed in Table 4-4.
69
Table 4-4 Pure gas permeability and selectivity for membranes with different
compositions at 35C ,45C and 55Ca
PH2d PN2d PCO2d CO2/H2 CO2/N2

b c
Sample T (C) Tm2p (C)
(Barrer) (Barrer) (Barrer) selectivity selectivity
35 33.4 6.25 275 8.2 44.0

GP w/o PEG 14.9
45 49.2 9.90 344 7.0 34.7
35 36.0 7.29 333 9.3 45.7
GPP400-20 20.5
45 53.1 11.7 413 7.8 35.3
35 37.4 7.54 363 9.7 48.1
GPP400-40 19.3
45 53.5 11.9 455 8.5 38.2
35 40.0 8.20 427 10.7 52.4
GPP400-60 20.0
45 53.8 12.9 479 8.9 37.1
35 41.5 8.40 383 9.2 45.8
GPP1000-20 35.2
45 61.0 13.4 474 7.8 35.4
35 55.0 11.2 540 9.8 48.2
GPP1000-40 41.7
45 79.5 18.3 662 8.3 36.2
35 65.9 14.3 696 10.6 48.7
GPP1000-60 45.0
45 86.6 20.4 845 9.8 41.4
35 25.2 4.30 178 7.1 41.4
GPP1500-20 43.3
45 67.5 14.4 509 7.5 35.3
35 20.4 3.32 141 6.9 42.5
GPP1500-40 46.8
45 70.3 16.0 566 8.1 35.4
35 9.30 1.38 55.6 6.0 40.3
GPP1500-60 48.5
45 96.0 22.3 809 8.4 36.3
35 20.1 3.31 139 6.9 42.0
GPP2000-20 45 46.2 38.1 8.70 274 7.2 31.4
55 97.0 22.7 604 6.3 26.6
35 18.0 3.01 128 7.1 42.4
GPP2000-40 45 52.3 38.9 8.50 285 7.3 33.7
55 111 23.0 749 6.7 32.6
35 11.5 1.70 68.0 5.9 40.0
GPP2000-60 45 54.7 25.8 4.73 163 6.3 34.5
55 143 34.1 1040 7.3 30.5
Semi-crystalline 35 1.8 0.24 13 7.2 54
28 68.0
PEO 45 6.4 0.99 40 6.3 40
70
a
55C was only employed for GPP2000 series
b
GPPX-Y represents the sample code, where X is the molecular weight and Y is the
weight percentage of PEG blended.
c
Peak melting temperatures of the 2nd heating curve
d
Permeability, 1 Barrer = 10-10 cm3 (STP).cm/cm2scmHg
The gas permeation performance of GP w/o PEG is comparable to the previous
work [10]. The reason of the higher H2 and CO2 permeability compared to the pure
semi-crystalline PEO is that the crystallinity of PEO segments in GP w/o PEG is
greatly suppressed by the cross-linking.
For GPP400 and GPP1000 series, both permeability and permselectivity are
improved at 35 C and 45 C, which is contradictory to the trade-off relationship of
glassy polymers. These membranes take the advantage of the higher solubility
selectivity of CO2 over H2 and N2 introduced by EO groups. As mentioned
previously, the EO group concentration determines the CO2/light gas selectivity. By
increasing the weight percentage of PEG400, the CO2/H2 permselectivity increases
from 8.2 (no PEG) to 10.7 (60 wt% PEG400) at 35 C. The CO2 permeability
increases by more than 50% at 35 C with 60 wt% of PEG400 in the matrix. The
diffusivity increment is the major driving force for the permeability improvement,
while the CO2 solubility shows little change with the addition of PEG400 and
PEG1000 as shown in Table 4-5. The liquid PEGs in the matrix greatly facilitates
71
the transportation of CO2, leading to an ultra-high diffusivity than the conventional
solid membranes.
Table 4-5 Gas permeability, solubility and diffusivity coefficient results compared
with PDMS and PEO from other sources
PCO2b SCO2 DCO2106

(Barrer) (cm3 STP/cm3 atm) (cm2/s)
Samplesa
35C 45C 35C 45C 35C 45C
GP w/o PEG 275 344 1.59 1.16 1.32 2.26
GPP400-20 333 413 1.47 1.15 1.72 2.73
GPP400-40 363 455 1.48 1.25 1.87 3.00
GPP400-60 427 479 1.50 1.19 2.17 3.05
GPP1000-20 387 474 1.51 1.17 1.93 3.07
GPP1000-40 540 662 1.65 1.27 2.48 3.97
GPP1000-60 696 845 1.65 1.25 3.20 5.14
GPP1500-20 178 509 1.14 1.24 1.19 3.12
GPP1500-40 141 566 0.82 1.27 1.31 3.39
GPP1500-60 55.6 810 0.54 1.31 0.78 4.68
GPP2000-20 139 274 0.99 1.19 1.07 1.76
GPP2000-40 128 285 0.74 1.22 1.32 1.77
GPP2000-60 68 163 0.46 1.29 1.13 0.96
Semi-crystalline
13 40 0.37 N/A 0.27 N/A
PEO28
Amorphous
143 N/A 1.3 N/A 0.86 N/A
PEO-3528
PDMS-3525 3800 N/A 1.3 N/A 22.2 N/A
72
a
GPPX-Y represents the sample code, where X is the molecular weight and Y is the
weight percentage of PEG blended.
b
1 Barrer = 10-10 cm3 (STP).cm/cm2scmHg
Upon surpassing the melting temperatures, GPP1500 and 2000 show tremendous
permeability jumps due to significant increments in both diffusivity and solubility
as listed in Table 4-5. Because of the existence of PEG crystals, the permeability of
all gases for GPP1500 series is smaller than that for GP w/o PEG at 35 C.
Nevertheless, the CO2 permeability rises by a factor of 10 after the crystals melt.
The CO2 permeability of GPP1500-60 increases from 55.6 Barrer at 35 C to 809
Barrer at 45 C. Within our expectation, the permeability of GPP2000 series is still
lower than GP w/o PEG even at 45 C, because PEG crystals do not fully melt. In
order to investigate the permeation properties of GPP2000 series in a liquid state,
the permeation cell is heated up to 55 C to facilitate the melting of PEG2000. A
similar permeability jump (from 68 Barrer at 35 C to 1040 Barrer at 55 C) is
observed. The melting point measured by DSC is slightly higher than that observed
from the permeation jumping. This difference could be caused by the temperature
lag in the dynamic DSC measurement.
Normally, the gas permeability will increase with increasing PEG content. On the
contrary, the permeability declines with increasing PEG content when PEG is in a
semi-crystalline form as shown in Figure 4-7. The main reason of this phenomenon
73
is that the PEG crystals are considered as impermeable domains for gases. In
addition, the shape, size and size distribution of the crystallites affect the tortuosity
and the chain mobility of the amorphous phase. Thus, the diffusivity decreases
when the impermeable crystals exist. Furthermore, semi-crystalline membranes
have less sorption sites than amorphous membranes. Sorption measurements reveal
that the CO2 solubility of GPP1500 and GPP2000 is smaller in the semi-crystalline
state as shown in Table 4-5. In conclusion, increasing PEG content in the
semi-crystalline membranes will lead to less amorphous regions and create more
complicated tortuosity for gas diffusion. Thus, the permeability decreases because
of the lower diffusivity and the lower solubility.
Figure 4-7 CO2 permeability of GPP series and GP w/o PEG at 35C (blank) and
45C (checked)
74
The permselectivity varies a lot when PEG content or temperature changes. For
membranes with liquid PEGs, the CO2/H2 permselectivity increases in pace with
the PEG content as shown in Figure 4-8 because of the increased EO concentration.
For membranes with PEG crystals, the CO2/H2 permselectivity decreases with
increasing PEG content, because the size sieving effect is enhanced by the
increasing tortuosity. In rubbery materials, the permselectivity usually weighs
heavier on solubility selectivity. Although H2 diffuses faster than CO2, the
permeability of CO2 is still much larger than H2 because of the higher solubility.
Diffusivity selectivity of CO2/H2 is usually below 1 due to the size sieving effect.
However, the CO2 diffusivity gains a lot upon traversing the melting point, leading
to a relative smaller diffusivity difference between CO2 and H2. Thus, the overall
selectivity is improved by minimizing the size sieving effect by melting the crystals.
As shown in Figure 4-8, the CO2/H2 permselectivity of GPP1500 series after PEG
crystals melting is improved to different extents depending on the PEG content in
the blends. GPP1500 with 60wt% PEG shows the greatest improvement from 6.0 to
8.4, while GPP2000 series show less CO2/H2 permselectivity improvement because
PEG2000 crystals only partially melt as indicated by the small melting peaks at
lower temperatures in Figure 4-9d.
75
Figure 4-8 Permselectivity at 35C (solid) and 45C (hollow) for CO2/H2
Figure 4-9 DSC curves for (a) GPP400, (b) GPP1000, (c) GPP1500 and (d)
GPP2000
76
Table 4-6 shows the CO2/N2 mixed gas results. A considerable CO2/N2 selectivity
decrease from 41.4 to 31.3 for GPP1000-60 and from 36.3 to 32.0 for GPP1500-60
at 45 C is observed. CO2 permeability is comparable with the pure gas permeability
for both samples. However, the N2 permeability increases from 20.4 to 26.8 Barrer
for GPP1000-60 and from 22.3 to 26.2 Barrer for 1500-60, respectively. These
phenomena are probably caused by the CO2 plasticization in the solubility
selectivity membranes [48].
Table 4-6 Mixed gas permeability and selectivity for GPP1000-60 and
GPP1500-60 at 45C
50:50 CO2/N2 mixed gas

CO2/N2
Sample PCO2 PN2 selectivity
(Barrer) (Barrer)
31.30.6
GPP1000-60 839 (845)* 26.8 (20.4)
(41.4)
32.00.5
GPP1500-60 838 (809) 26.2 (22.3)
(36.3)
*Number between brackets is the permeability and permselectivity tested by pure gases.
4.2.5 Effect of Testing Temperature
The effect of testing temperature on CO2 permeability of GPP1500-60 is
illustrated in Figure 4-10. The CO2 permeability increases from 26 Barrer at 30C to
77
860 Barrer at 55C. The temperature dependence of permeability without thermal
transition can be described by an Arrhenius type expression P P0 exp( E P / RT ) .
These linear relationships are only observed at lower temperatures and higher
temperatures. In between these two regions, a jump of permeability is observed near
the onset melting temperature, as shown in Figure 4-10. Mogri and Paul [49, 50]
have also observed a change in permeability of two orders of magnitude when the
side chains of poly(octadecyl acrylate) melt. Hirayama et al.[33] and Kim et al.[51]
have also observed an abrupt increase of permeability when PEG melt in their PEG
based materials. Nonlinear relationships appear with the thermal transition, because
Ep is changed, as well as the three parameters shown in equation (2-17). The
decrease of the activation energy for diffusion could be caused by the change of
diffusion mechanism from the hopping diffusion to the liquid-like diffusion. The
diffusivity of gases in the polymer melt could reach the diffusive limit on a time
scale similar to that of the polymer melt. Meanwhile, the tortuosity will be
minimized, and the chain motion in the amorphous region will be no longer affected
by the crystallites. There is a 6 times increment in diffusivity of GPP1500-60 at
45C compared to 35C, as shown in Table 4-5. The absolute value of condensation
enthalpy will not change because it is determined by the penetrants themselves.
However, the mixing enthalpy of CO2 and PEO based polymers will be more
negative because less energy is needed to allow CO2 molecules penetrate into the
matrix. Thus, the solubility increases when a thermal transition happens.

78
Afterwards the solubility will decrease when the temperature further increases.
The solid lines in Figure 4-11a and 4-11b represent the CO2 sorption isotherms
and the solubility coefficients of GPP1500 series and GP w/o PEG at 35C, while
the dashed lines represent the sorption at 45 C, respectively. The solubility
coefficients increase from 0.54, 0.82 and 1.14 to 1.31, 1.27 and 1.24 cm3
(STP)/cm3atm for GPP1500-60, GPP1500-40 and GPP1500-20 after melting,
respectively. Being the membrane with the highest crystal content, GPP1500-60
shows the lowest solubility coefficient close to that of the semi-crystalline PEO at
35C as shown in Figure 4-12b. On the contrary, the solubility coefficient of GP w/o
PEG decreases from 1.59 to 1.16 cm3 (STP)/cm3atm when temperature increases
because there is no thermal transition. For the same reason, GPP1000 series, in
which PEG1000 crystals already melt at both temperatures shows a solubility loss,
as shown in Table 4-5. However, the diffusivity increment overweighs the slight
decrease of solubility. Therefore, the permeability still shows considerable
enhancement at 45C. CO2 permeability of GPP1000-60 increases from 696 Barrer
to 845 Barrer despite its solubility decreases from 1.65 to 1.25 cm3 (STP)/cm3atm.
The solubility of GPP1000 series at 35 C could reach 1.5~1.6 cm3 STP/cm3 atm,
which is comparable with the solubility of amorphous PEO [28] (1.3 cm3 STP/cm3
atm) as shown in Figure 4-12b and the crosslinked PEO rubber [26] (1.5 cm3
STP/cm3 atm). The solubility of GPP2000 series increases from 0.46~0.99 to

79
1.19~1.29 cm3 (STP)/cm3atm due to the partial melting as indicated by the small
melting peaks as shown in Figure 4-9d.
Figure 4-10 Change of CO2 permeability of GPP1500-60 from 30C to 55C

*Tm2o is the onset melting temperature of PEG1500 in GPP1500-60 during 2nd
heating.
Figure 4-11 CO2 Sorption isotherm (a) and solubility coefficient (b) of GPP1500 at
35C and 45C
80
Figure 4-12 Sorption isotherm (a) and solubility (b) of GPP1500, PDMS [52]
semi-crystalline PEO and amorphous PEO [28] at 35C
4.2.5 Effect of PEGs Molecular Weights
Figure 4-13 shows the solubility and diffusivity of blended membranes
containing 40 wt% PEGs at 45 C. The CO2 solubility for these membranes varies
little as they have the same PEG content, while the CO2 permeability changes
dramatically. GPP1000-40 has the highest diffusivity while GPP2000-40 is the
lowest. For other samples with different contents of PEGs, the trend is almost the
same. The lowest diffusivity of GPP2000-40 can be ascribed to the partial melting
of the PEG crystals. However, the diffusivity difference among GPP400-40,
GPP1000-40 and GPP1500-40 could only be ascribed to the molecular weight
difference, because these PEGs are already in liquid states. Due to the technical
limitation, there is no suitable characterization method available to monitor the
effect of molecular weight on the diffusivity coefficient above the melting
81
temperature. An alternative method, by analyzing the crystallization and melting
behavior of the blend membranes, is an important way to understand this
phenomenon. Although melting is observed from DSC, we could still assume that
liquid PEG molecules in the matrix only vibrate violently in the confined
environment rather than free flowing. Extensive studies have been done in the past
decades to understand the crystallization behavior of low molar mass PEGs. It is
well known that PEG with a low molecular weight (Mw 3000 g/mol) crystallizes
exclusively with extended chains under normal cooling rate [53, 54]. In this
scenario, we propose a possible crystallization mechanism as depicted in Figure
4-14. PEGs with different molecular weights will have different orientations and
alignments in the confined environment. During membrane fabrication, PEGs are
heated to 70 C to surpass their melting temperatures so that the equilibrium could
be reached between the PEO segments of the matrix and the liquid PEG molecules.
The compatibility between the PEO segments and the PEG molecules is fairly good
so that they crystallize together upon cooling. All the membranes present one
crystallization peak during second cooling, although some of the membranes have
two melting peaks as shown in Figure 8a-d. Analysis on the heat of crystallization
in Table 2 also supports the assumption of co-crystallization. Hc is the heat of
crystallization obtained experimentally from the integration of DSC peak area. Hc
is the theoretical value calculated from
H c ' H c (PEG) wt %(PEG) H c (matrix) (1 wt %(PEG)) (4-1)

82
Hc and Hc values of GPP1000, 1500 and 2000 series are almost the same. For
GPP400 series, Hc is smaller than Hc, revealing that GPP400 series is easier to
crystallize. Crystallization temperatures of GPP400 blends, which are higher than
both GP w/o PEG and PEG400, also provide strong evidence for the conclusion that
GPP400 series has the strongest interactions with the PEO segments in the matrix.
Thus, the diffusivity of GPP400 series should be the lowest due to its highest
tendency to crystallize. This correlates well with the result obtained from sorption
experiments. The high concentration of hydrogen bonding of PEG400 may be the
reason of their strong crystallization tendency.
Figure 4-13 Solubility (square) and diffusivity (circle) of hybrid membranes

containing 40 wt% of PEG with different molecular weights at 45C
83
Figure 4-14 Crystallization of PEO segments and PEGs with different molecular
weights
In GP w/o PEG, PEO segments cannot fully crystallize due to cross-linking. A
shoulder peak, rather than a symmetric exothermic peak in the cooling curve is
observed, indicating that a considerable amount of imperfect PEO crystals are
formed because of the confinement. The crystallization peaks of GPP1000, 1500
and 2000 are located in between the peaks of the GP w/o PEG and the respective
pure PEGs. The fully extended PEG chains may facilitate the PEO segments of the
matrix to crystallize by reducing the extra free energy required to align chain
segments. Thus, the crystallization temperature increases with PEG content.
Crystal defects and lots of chain ends are created during crystallization because of
different chain lengths as illustrated in Figure 4-14. Several PEG400 molecules
could be aligned along one PEO segment (Mw1300). However, only one
PEG1000 chain is allowed to align along the PEO segment because of their similar
84
molecular weights and chain lengths. Once one PEG1000 chain is aligned with the
PEO segment, the remaining portion of the PEO segment may not arrange regularly,
thus leading to more defects. Therefore, the diffusivity of GPP1000 series is the
highest. The PEO segments of the matrix could be fully coupled with PEG1500
because of their similar chain lengths. One folding may exist when PEG2000 is
employed, because its chain length almost doubles that of the PEO segment. The
diffusivity of GPP1500 is slightly lower than that of GPP1000 at 45 C, because
fewer defects are created.
Summary
In this chapter, a novel method of employing liquid PEG as a gas separation
medium is introduced. The PEO-silica organic-inorganic network synthesized by
the sol-gel process has been proved to be an effective matrix for holding liquid PEG.
The permeability has been improved more than twice without losing
permselectivity when PEG with a proper molecular weight is employed. With the
loading of PEG molecules, CO2/H2 and CO2/N2 permselectivity is found to increase
by more than 10%. A significant permeability jump is observed when the testing
temperature surpasses the melting point of PEG. The diffusivity increment is
considered as the major contributor to the permeability jump, while the solubility
shows little change if there is no thermal transition. A considerable increase of

85
solubility coefficient is observed when solid PEG becomes liquid. Four PEGs with
different molecular weights have been investigated. PEG1000, which has a similar
molecular weight to the PEO segments in the PEO-silica organic-inorganic matrix,
is proved to be the best candidate to improve both CO2 permeability and CO2/light
gas permselectivity.
86
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95
CHAPTER 5 The Effect of End Groups and Grafting on
the CO2 Separation Performance of Polyethylene Glycol
Based Membranes
J. Xia, S. Liu, T.S. Chung, The effect of end groups and grafting on the CO2
separation performance of polyethylene glycol based membranes,
Macromolecules, 44 (2011) 7727-7736
96
Abstract
Rubbery membranes have attracted significant attention for the CO2/light gas
separation due to their high permeability and high solubility selectivity. This
chapter reports universal strategies to tailor CO2 permeability and CO2/light gas
permselectivity via blending or grafting of poly (ethylene glycol) (PEG)
derivatives into or onto organic-inorganic membrane (OIM) substrates. A PEG
derivative is blended into the substrate, which contains inorganic siloxane
networks and poly(ethylene oxide) segments, followed by thermal grafting. Ultra
high CO2 permeability (982 barrer at 45 C) was obtained via physical blending,
while an extremely high CO2 permeability (1840 barrer at 45 C) was obtained
after chemical grafting. Neither of these two modification methods shows a loss of
CO2/H2 and CO2/N2 selectivity compared to the substrate. Melting and
crystallization behavior of this PEG derivative are believed to significantly affect
the overall gas permeation performance. All the features make these OIMs
promising membrane materials for CO2 capture.
97
5.1 Introduction
In chapter 4, the separation performance of OIMs was successfully enhanced
by using a physical blending method [1].These OIMs with PEG up to 60 wt%
demonstrated CO2 permeability of 845 barrer with CO2/H2 and CO2/N2
permselectivity around 10 and 40, respectively. However, their performance could
still be further improved by eliminating hydrogen bonding using non-hydroxyl
groups as the end groups according to the trend reported by Yave at al. [2]. By
modifying OIMs with O-zone initiated polymerization of poly(ethylene glycol
methacrylate) (PEGMA), Lau et al. [3] have achieved a CO2 permeability of 1920
barrer in mixed gas permeation tests. Thus, in this chapter two kinds of
methoxy-PEG-azide (Mw = 350 and 1100) have been employed to replace PEG for
comparison of end groups. Furthermore, azide functional groups provide the
freedom to investigate the effect of PEG grafting on the overall gas permeation
performance because they are reactive to the C-H bond. Due to the high
crystallization tendency of higher molecular weight PEG, OIMs with
PEG-azide1100 are not amorphous at ambient temperature. Therefore, the
investigation of temperature dependence of gas permeation has also been carried
out.
98
5.2.1 Basic Physicochemical Properties
These reverse-selective OIMs are constructed by employing the in situ formed
siloxane inorganic networks as the crosslinking junctions. The organic segments
containing PEO chains are immobilized by these inorganic contents, as shown in
Figure 3-3. The inorganic components (black spots) are dispersed homogenously in
the organic phase as indicated by the TEM micrograph in Figure 5-1a. The lattice
features inside of the black spots as shown in Figure 5-1b prove that the inorganic
siloxane networks have been successfully synthesized. The micromorphology
analysis in details regarding to the shape and the size distribution could be found in
our previous work [1]. PEG-azides of Mw350 and Mw1000 were blended into the
pristine substrate (also referred as GP w/o PEG-azide). The blended hybrid OIMs
are labeled by GPAX-Y, in which GPA represents the GOTMS-PEO PEG-azide
blend, X represents the molecular weight of blended PEG, and Y represents the
weight percentage of the blended PEG. For example, GPA1100-20 means the OIM
contains 20 wt% of PEG-azide 1100g/mol.
99
Figure 5-1 TEM micrography of GP w/o PEG-azide at (a) a low magnitude and (b)
a high magnitude
It is well known that PEGs and their derivatives have a strong crystallization
tendency due to the highly polar ethylene oxide moieties. Meanwhile, the melting
temperatures and crystallization temperatures of these PEG based materials are
close to the ambient temperature, which makes the thermal history of these OIMs
very unclear. Therefore, all the OIMs employed in this study were cooled to -20C
first and then naturally warmed up to ambient temperature prior to characterization.
Because of the cooling induced crystals, GPA1100 series are translucent even at
ambient temperature due to the relative high melting temperature of
PEG-azide1100 (above 25 C), as shown in Table 5-1. The membranes of GP w/o
PEG-azide and GPA350 series are transparent due to their lower melting
temperatures (below 25 C).
100
Table 5-1 Thermal properties of GPA1100 series
Samples Tg (C) Tm2p (C)a Tc2p (C)b -Hc (J/g)c -Hc (J/g)d
GP w/o PEG-azide N/A 24.5 -24.5 51 N/A
GPA1100-20 -51.9 41.1 2.5 76 71
GPA1100-40 -54.2 42.1 16.1 95 91
PEG-azide1100 NA 45.1 22.5 153 N/A
[a] Peak melting temperature of the 2nd heating curve

[b] Peak crystallization temperature of the 2nd cooling curve
[c] Hc is the heat of crystallization obtained experimentally from DSC
[d] Hc is the theoretical value calculated by equation 5-1
5.2.2 Gas Transport Properties of OIMs with Physical Blending
Previous studies show that both CO2 permeability and CO2/H2 selectivity can
be enhanced by adding a low molecular weight PEG into an existing CO2 selective
material [1, 2, 4-9]. However, this kind of enhancement reaches a limit when
hydroxyl terminated PEG (normal PEG) is employed. The high cohesive energy
caused by the hydrogen bonding between the hydroxyl groups and the EO groups
inhibits further improvement on the CO2 diffusivity. In this work, PEGs terminated
with methoxy group and azide group are used to replace the normal PEG.
According to the previous work [1], the molecular weight of the blended PEG has a
significant effect on the gas permeation performance. Therefore, only PEG-azides
101
with similar molecular weights are used. GPA350 and GPA1100 series (here A
represents PEG-azide) are compared with GPP400 and GPP1000 series in our
previous work (the last P represents PEG), respectively. For easy comparison, only
the permeability data when the membranes are in amorphous status are listed
(Table 5-2).
Table 5-2 Pure gas permeability and selectivity of OIMs blended with PEG-azide
H2 N2 CO2
Temperature CO2/H2 CO2/N2
Sample permeability permeability permeability
(C) selectivity selectivity
(barrer)a (barrer) (barrer)
GP w/o 35 33 6.3 275 8.2 44

PEG-azide 45 49 9.9 344 7.0 35
b
35 54.5 (36) 12.6 (7.3) 530 (333) 9.5 (9.3) 41 (46)
GPA350-20
45 77.5 (53) 19.3 (11.7) 634 (413) 8.2 (7.8) 33 (35)
35 70.7 (37) 20.4 (7.5) 750 (363) 10.6 (9.7) 37 (48)
GPA350-40
45 101 (54) 29.8 (11.9) 913 (455) 9.0 (8.5) 31 (38)
GPA1100-20 45 62 (61) 13.9 (13.4) 468 (474) 7.5 (7.8) 34 (35)
GPA1100-40 45 91 (80) 22.6 (18.3) 982 (662) 10.8 (8.3) 43 (36)
[a] 1 Barrer = 10-10 cm3 (STP).cm/cm2scmHg

[b] data in the blanket are from chapter 4 where PEG 400 and 1000 were used. In
other words, GPA350 and GPA1100 series are compared with GPP400 and
GPP1000 series, respectively.
With the addition of PEG-azide, the permeability of CO2 as well as other gases
shows surprising increments of up to 100%, compared to those blended with
normal PEG. The permeability improvement increases with more loading. Sorption
102
studies show that solubility is enhanced with more PEG-azide loading. Diffusivity
calculated based on the solution-diffusion mechanism shows improvement as well.
The solubility enhancement could be attributed to a higher EO group density, while
the diffusivity increment could be ascribed to the increasing chain flexibility, as
indicated by the decreasing glass transition temperature as shown in Figure 5-2.
Figure 5-2 Glass transition temperature shifts of GPA1100 series by DSC
The permeability increment of samples with lower molecular weights
(GPP400 to GPA350 series) is greater than that of the higher molecular weight
samples (GPP1000 to GPA1100 series) after replacing hydroxyl groups with azide
groups. This is due to the fact that the end group concentrations are higher in
GPA350 and GPP400 than those in GPA1100 and GPP1000 at the same loading.
103
Without hydrogen bonding, the chain flexibility increases, thus the diffusivity of
CO2 in GPA350 and GPA1100 increases, as shown in Table 5-3. The CO2 solubility
of GPA1100 series also increases slightly compared to that of GPP1000 series,
because more EO moieties are able to interact with CO2 after eliminating hydrogen
bonding. The CO2/H2 permselectivity increases because of the increased solubility
selectivity. On the other hand, the size sieving effect has also been weakened
because the polymer chains are more flexible after eliminating hydrogen bonding.
The slight decrease of CO2/N2 selectivity except GPA1100-40 is ascribed to the
weakened size sieving effect, because the kinetic diameter of CO2 (3.3) is smaller
than that of N2 (3.64 ). The solubility and diffusivity of OIMs blended with 20 wt%
PEG and PEG-azide are almost the same because the effect of replacing the end
group is not so obvious due to their low PEG loadings.
Table 5-3 Solubility and diffusivity coefficients of GPA1100 and GPP1000 series at
45 C
SCO2 DCO2
3 3
PEG blended (%) (cm STP/cm atm) (cm2/s)x106
GPP1000 GPA1100 GPP1000 GPA1100
0 1.16 1.16 2.26 2.26
20 1.17 1.17 3.07 3.05
40 1.27 1.29 3.97 5.79
GPA1100-40 is also evaluated by a binary gas mixture of CO2/N2 (50:50 mole

104
fraction) at 45 C. Similar to our previous work [1], CO2 permeability (998 barrer)
is comparable to that of the pure gas (982 barrer), while the N2 permeability
increases from 22.6 barrer to 31.5 barrer. Therefore, the CO2/N2 selectivity
decreases from 43 to 32, which is caused by the CO2 plasticization [10].
5.2.3 Thermal Properties of GPA1100 Series
Thermal properties of polymeric membranes are critical to the gas permeation
performance. This is especially true for the PEO-based rubbery membranes,
because they are highly crystallizable materials and their melting temperatures are
close to the normal permeation testing temperatures, 35 C. Because of their
structure similarity, PEG-azide and PEO segments of GP w/o PEG-azide could
crystallize with each other as revealed by the heat of crystallization analysis. In
Table 1, Hc is the heat of crystallization experimentally obtained from DSC, while
Hc is the theoretical value calculated using Equation 6 by assuming
co-crystallization.
H c ' H c (a) wt %(PEG - azide) H c (b) (1 wt %(PEG - azide)) (5-1)
where Hc(a) is the heat of crystallization of pure PEG-azide, Hc(b) is the heat of
crystallization of GP w/o PEG-azide. The experimental value is comparable to the
theoretical value. Figure 5-3a and 5-3b are the 2nd heating and 2nd cooling DSC
curves of GPA1100 series. GP w/o PEG-azide and pure PEG-azide1100 are also
105
included for comparison. A melting point depression (MPD) is observed for
GPA1100 series as shown in Table 5-1. Similar to the crystallization behavior of
crystallizable block copolymers, the MPD in our case could be caused by the
confined crystallization of PEG-azide in the OIMs [11]. The extending of the
PEG-azide crystals is restricted by the cross-linked network, which would result in
a decrease of the melting temperature. The crystallization peaks of GPA1100 series
are located between the peaks of GP w/o PEG-azide and pure PEG-azide. That the
lowest crystallization temperature belongs to GP w/o PEG-azide indicates its
lowest crystallization tendency, because the PEO segments in the GP w/o
PEG-azide are immobilized by crosslinking. When PEG-azide1100, which has a
similar molecular weight to the PEO segments in the matrix, is added into the
matrix, co-crystallization happens. PEG-azide1000 plays a role of crystallization
intermediate between two PEO segments so that the membrane becomes easy to
crystallize. When more PEG-azide is added, the crystallization tendency increases,
thus resulting in a higher crystallization temperature as seen in Figure 5-3b.
106
Figure 5-3 DSC curves of (a) 2nd heating and (b) 2nd cooling of GPA1100 series
5.2.4 Temperature Dependence of Gas Permeation Properties
For a temperature range that does not involve thermal transition, there is a
logarithmic relationship between permeability P and 1/T, which could be described
by a vant Hoff-Arrhenius equation (equation 2-16). Only few researchers had done
their research in the temperature range that involves the thermal transition. Mogri
and Paul [12, 13] developed a system to monitor the permeability change before
and after side chain melting in acrylates. They found that both diffusivity and
solubility increased above the melting temperature due to lower diffusion activation
energy in the molten state and an increase in sorption sites. Okamoto et al. [14],
Hirayama et al. [15], and Kim et al. [16] have individually observed the
discontinuity in the lnP versus 1/T curve in their PEO-based polymer systems.
Abrupt points around the melting temperatures indicate that the permeability jumps
could be attributed to the melting of PEO crystals. However, detailed analyses on
107
the temperature dependence of the selectivity, especially for the CO2/H2 selectivity,
have not been addressed.
Figure 5-4 shows the temperature dependence of permeability measured at
30-50 C and 2 atm. A similar permeability discontinuity is observed, especially for
those with a higher PEG-azide loading. Below the melting temperature, PEG-azide
crystals are impermeable physical obstacles that impede gas transport. In addition,
the existence of crystalline domains restricts the chain motion in amorphous
regions. Thus, the permeability declines with increased crystallinity. GPA1100-40
shows the lower permeability below the melting temperature, while GPA1100-20
has a higher permeability. After the crystals melt, the permeability increases with
increasing EO group concentration. Therefore, the permeability trend above the
melting temperature is reversed. For GPA1100-40, the CO2 permeability could
reach as high as 1052 barrer at 2 atm and 50 C. Permeability jumps happen
between 35 and 40 C; however, the melting points measured by DSC are larger
than 40 C as shown in Table 1. This may be caused by the temperature lag in the
dynamic DSC measurement, as well as the facilitated melting at the presence of
compressed CO2 (discussed later) [17].
108
Figure 5-4 The temperature dependence of CO2 permeability of GPA1100 series
Figure 5-5a and b present the temperature dependence of CO2 sorption
isotherms of GPA1100-20 and GPA1100-40. Most of isotherm curves are linear,
except for GPA1100-40 at 35 C, where the sorption isotherm curves show a
nonlinear trend when the pressure increases. The nolinear sorption isotherm may
be explained by the CO2 induced plasticization [10, 17]. The dissolved CO2 in the
polymer matrix disassociates polymer chains, thus lowering the melting
temperature of PEG-azide. Simultaneously, more effective EO groups are released
because of the melting, which further increases the sorption of CO2. When the
loading of PEG-azide is low, this phenomenon is not obvious. However, when the
PEG-azide content increases, plasticization causes sorption increases so that the
109
GPA1000-40 isotherm shows an upward trend at 35 C. The solubility coefficient
for the linear sorption isotherm is obtained by fitting the slope, while dC/dp at 2 atm
is used to calculate the solubility for the nonlinear isotherms. Figure 5-6a shows the
temperature dependence of CO2 solubility and N2 solubility. Typical shaped
curves of solubility are observed for CO2, while the N2 solubility always increases
with increasing temperature [15]. Below the melting temperature, the solubility is
proportional to the volume fraction of amorphous regions, the solubility therefore
decreases with more PEO-azide loading (i.e., higher overall crystallinity). After the
crystals melt, this trend is reversed because OIMs with more liquid PEO-azide have
more EO groups favorable for CO2 sorption. When the temperature further
increases, CO2 solubility decreases because the heat of sorption ( H s ) is negative in
PEO based membranes [15, 16]. N2 solubility of these OIMs always increases
despite of the thermal transition because H s is always positive for N2 [15, 16]. H2
sorption in this kind of material is too low to be measured accurately. However, we
believe that the H2 solubility would not change too much when the temperature
varies. Figure 5-6b shows the temperature dependence of CO2 diffusivity in
GPA1100-20 and GPA1100-40. The diffusivity below the melting points is
comparable. Nevertheless, the diffusivity of GPA1100-40 increases tremendously
after PEG-azide melts because of the high PEG-azide content. The temperature
dependence of the solubility and diffusivity may be further related to the CO2/H2
and CO2/N2 permselectivity as shown in Figure 5-7a and b. GPA1100-20 shows the
110
highest CO2/H2 permselectivity at 40C, at which the temperature the highest CO2
solubility is obtained. It is believed that the highest permeability selectivity comes
from the highest solubility selectivity, because the selectivity in rubbery materials is
governed by the solubility selectivity. With more EO groups, the solubility
selectivity increases, thus resulting in a high selectivity of GPA1100-40 (12.3) than
that of GPA1100-20 (8.5). CO2/N2 permselectivity always declines with rising
temperature due to the decreasing CO2/N2 solubility selectivity and the weakened
size sieving effect.
Figure 5-5 Temperature dependences of CO2 sorption isotherms of (a)

GPA1100-20 and (b) GPA1100-40
111
Figure 5-6 Temperature dependence of (a) solubility and (b) CO2 diffusivity of
GPA1100-20 and GPA1100-40
Figure 5-7 Temperature dependence of (a) CO2/H2 and (b) CO2/N2 selectivity of
GPA1100-20 and GPA1100-40
5.2.5 Thermal Grafting of PEG-azide and Characterizations
Azido groups are linear 1, 3-dipolar structures that could easily form nitrenes,
which are highly reactive and short-lived nitrogen intermediates, with the presence
of ultraviolet radiation or heat. Nitrenes have four nonbonded electrons so that they
112
are able to insert into C-H bonds, following the reactivity order of tertiary >
secondary > primary C-H bonds [18, 19]. The most possible thermal grafting
mechanism is shown in Figure 3-3. The activated nitrenes attack the tertiary C-H
13
bonds of PPO segments and form C-N bonds at 140 C under vacuum. C solid
state NMR spectra in Figure 5-8 show the chemical environment change after
thermal grafting. By comparing Figure 5-8a (GPA1100-40 pristine) and Figure 5-8b
(GPA1100-40 after thermal grafting), small peaks belonging to -CH2-N3 (g; =
51ppm) [20] disappear, indicating that azide groups are fully reacted. This
correlates well with the nitrogen 1s binding energies change characterized by XPS
as shown in Figure 5-9. Before thermal grafting, two distinct peaks (405 eV and
401 eV) with a peak areas ratio of 1:2, are assigned to the central, electron-deficient
nitrogen and the other two nitrogen atoms in the azide group, respectively [21]. A
small shoulder peak at 399 eV corresponding to the organic C-N bond [21] is also
observed due to the existence of amine groups during matrix synthesis. Reaction of
nitrenes with C-H bonds via insertion reduces the 401 eV and 405 eV peak to the
level of noise. However, the intensity or the peak area of the C-N bond increases
after thermal grafting, thus indicating the successful conversion of C-N3 groups into
C-NH groups. Peak c ( = 70.3 ppm) in Figure 5-8a and b is normally assigned to
the CH2 of PEG, while peak d ( = 74.8 ppm) and e ( = 71.7 ppm) are assigned to
CH2 and CH of poly (propylene glycol) [22]. Peak a ( = 9.07 ppm), peak f ( = 17.0
ppm) and peak b ( = 22.9 ppm) at a lower value are assigned to the carbons of the
113
aliphatic part as shown in Figure 5-8a and b. After PEG-azide grafting, the relative
intensity of the CH moiety (peak e) decreases and a small shoulder peak at a higher
value is observed. Part of e-type carbons are connected to the nitrogen atoms,
which are more electronegative than the hydrogen atoms. Thus, a chemical shift of
the carbon atoms at the grafting point moves to a higher value. Other types of
13
grafting have not been seen in C-NMR spectra, which might be caused by their
relative low reactivity and the low sensitivity of solid state 13C NMR. At 140 C,
only grafting reactions are activated. The self-decomposition of PEG-azide1000
starts at 240 C as seen from TGA in Figure 5-10.
Figure 5-8 13C solid state NMR spectra of (a) GPA1100-40 pristine and (b)
GPA1100-40 after thermal grafting
114
Figure 5-9 N1s XPS data before and after thermal grafting for GPA1100-40
Figure 5-10 TGA data of GPA1100-40 before thermal grafting
115
5.2.6 Gas Permeation Properties After Thermal Grafting
Gas permeability is almost doubled and the selectivity only slightly decreases
after thermal grafting as depicted in Table 5-4. The highest CO2 permeability
obtained is 1840 barrer with CO2/H2 and CO2/N2 selectivty of 8.3 and 36 at 2 atm
and 45 C. Compared to the pristine substrate (GP w/o PEG-azide), the permeability
is almost improved by 5-fold and the selectivity even slightly increases. With PEG
grafting on the backbone of OIMs, the crystallization tendency is greatly depressed
because PEG-azide is partially immobilized. The polymer chains of the blended
PEG cannot be rearranged easily and will create lots of chain ends and voids within
the mesh of the OIMs. Therefore, the diffusivity will increase due to more free
volume created by these irregular chain ends and voids. Figure 5-11 shows the CO2
diffusivity and solubility changes after thermal grafting of GPA1100-40. The CO2
diffusivity shows a great improvement at any temperature. However, the CO2
solubility shows enhancement only below the melting temperature in pristine
GPA1100-40. Above the melting point, the solubility is slightly lower than that
before grafting. This could be ascribed to the partial immobilization of PEG-azide.
Fewer EO groups are involved in the CO2 sorption because some of the EO groups
are not available due to the steric hindrance. The increment of solubility at 30 and
35 C could be attributed to the amorphous nature of GPA1100-40 after grafting.
Figure 5-12 shows the WXRD patterns at ambient temperature of GP w/o
116
PEG-azide, GPA1100-40 before and after grafting. GP w/o PEG-azide is
amorphous because of the cross-linked structure. GPA1100-40 is a semi-crystalline
membrane at room temperature, which has two characteristic crystal peaks of PEO
located at 2 = 19.2 and 23.3 [23]. With the PEG grafting, GPA1100-40 does not
shows obvious crystal peaks. DSC cooling curves have also revealed the suppressed
crystallization tendency after grafting as shown in Figure 5-13. The crystallization
temperatures of GPA1100-20 and GPA1100-40 drop from 2.5 C and 16.1 C to
-13.4 C and 8.5 C after grafting, respectively. Exclusion from crystallization at
ambient temperature makes these OIMs more valuable for CO2 separation in a
broad temperature range. These preliminary results have shown a promising
method to further improve CO2 permeability of the OIMs.
Table 5-4 Pure gas permeability and selectivity of GPA1100 series before and after
grafting
H2 N2 CO2
Temperature CO2/H2 CO2/N2
Sample permeability permeability permeability
(C) selectivity selectivity
(barrer)[a] (barrer) (barrer)
35 36.7 7.54 321 8.7 43
GPA1100-20
45 62.3 13.9 468 7.5 34
GPA1100-20 35 70.4 13.6 595 8.5 44

after grafting 45 106 19.4 695 6.6 36
35 22.0 4.62 247 11.2 53
GPA1100-40
45 91.0 22.6 982 10.8 43
GPA1100-40 35 61.1 10.5 513 8.4 49
after grafting 45 222 50.5 1840 8.3 36
[a] 1 Barrer = 10-10 cm3 (STP).cm/cm2scmHg

117
Figure 5-11 CO2 solubility (open) and diffusivity (solid) of GPA1100-40 before
and after grafting
Figure 5-12 Wide angle XRD patterns of GP w/o PEG-azide, GPA1100-40 before
and after the grafting at ambient temperature
118
Figure 5-13 2nd cooling curve of GPA1100-20 and GPA1100-40 before and after
the grafting
Summary
This chapter explored strategies to increase the CO2 permeability without
sacrificing the selectivity for the CO2 selective OIMs. PEG terminated with one
azide and one methoxy group tends to enhance the CO2 permeability by a factor of 2
compared to hydroxyl end groups. A permeability jump is observed when the
temperature surpasses the melting point of PEG-azide. The temperature
dependences of permeability, solubility, diffusivity and selectivity are discussed in
detail. Maxima of CO2 solubility and CO2/H2 permselectivity are obtained in a
given temperature range. Attempt to graft PEG chains onto the backbone of the
119
13
OIMs via azide reaction has been made. Solid state C-NMR, XPS and TGA
indicate that the PEG-azide has been successfully grafted. The CO2 permeability
increases by 5-fold for grafted membranes as compared with the un-grafted
substrate. The crystallization tendency of the grafted membrane has been greatly
depressed. Diffusivity increment is believed to be the major reason for the
permeability enhancement. Extremely high CO2 permeability makes these OIMs
great potential as commercial membrane materials for CO2 capture. However, it is
still a long way to fabricate these materials into hollow fibers or asymmetric
membranes with a separation layer thickness in the range of 100 nm. Studies on
making these materials into multilayer thin film composite membranes by
continuous coating [24, 25] are ongoing in our group. Because PEO-based
materials are hydrophilic and mechanically weak compared to the conventional
glassy polymers, future studies focused on the long-term stability under water
vapor exposure and various gas mixture feeds are critical to the next step of
development.
120
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Measurements for Side-Chain Crystalline Polymers, Journal of Membrane
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[13] Z. Mogri, D.R. Paul, Gas Sorption and Transport in Side-Chain Crystalline
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and Crosslinked Polymer Films, Journal of Membrane Science, 160 (1999)
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[16] J.H. Kim, S.Y. Ha, Y.M. Lee, Gas Permeation of Poly(Amide-6-B-Ethylene
Oxide) Copolymer, Journal of Membrane Science, 190 (2001) 179-193.
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Dilation, and Transport Properties of Polysulfone, Journal of Polymer
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[18] B.T. Low, T.S. Chung, H. Chen, Y.C. Jean, K.P. Pramoda, Tuning the Free
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124
CHAPTER 6 Aging and Carbon Dioxide Plasticization of
Thin Extem XH1015 Polyetherimide Films
J. Xia, T.S. Chung, P. Li, N. Horn, D.R. Paul, Aging and carbon dioxide plasticization in
thin polyetherimide films, Polymer, 53 (2012) 2099-2108
125
Abstract
Industrial gas separation membranes have selective dense layers with
thicknesses around 100 nm. It has long been assumed that these thin layers have the
same properties as thick (bulk) films. However, recent research has shown that thin
films with such thickness experience accelerated physical aging relative to bulk
films and, thus, their permeation properties can differ significantly from the bulk.
Thin films made from Extem XH 1015, a new commercial polyetherimide, have
been investigated by monitoring their gas permeability. The permeability of the thin
films is originally greater than the thick films but eventually decreases well below
the permeability of the thick film. The CO2 plasticization of Extem thin films is
explored using a series of exposure protocols that indicate CO2 plasticization is a
function of film thickness, aging time, exposure time, pressure and prior history.
126
6.1 Introduction
Glassy amorphous polymers are of interest as gas separation membrane
because of their good balance of permselectivity versus permeability [1]. During
the past three decades, hundreds of commercial or lab synthesized glassy polymers
have been screened for certain separation applications by evaluating their gas
permeability in the form of thick dense films [2]. This is the very first step to select
an appropriate material to develop a commercial membrane, e.g., asymmetric
hollow fibers. From the perspective of productivity, the thickness of the dense thin
selective layer of hollow fiber membranes should be no more than a few hundred
nanometers. Due to the limitation of characterization techniques, the thickness of
this dense layer of asymmetric membrane is usually obtained by dividing the gas
permeability measured on a thick film by the permeance of the fabricated
membrane rather than by direct measurement. This assumes that the dense thin
selective layers (~100 nm) at the surface of the hollow fiber have the same
permeability as thick dense films (~20 m or more). However, a good deal of work
from this laboratory over the past decade has shown that this assumption is not valid
since the gas permeability of thin films is not only a function of thickness but also a
function of time [3-21]. As a result, thick dense film data do not give a full picture
of material performance as gas separation membranes.
127
A thermodynamic equilibrium state is not established when polymers are
cooled below their glass-transition temperature (Tg). The super-cooled polymer
liquid possesses a relatively high free volume because of the frozen in polymer
segment packing. However, these materials slowly progress towards an equilibrium
state [22] by the process called physical aging. The observed aging rate becomes
much faster as the film becomes thinner for reasons that are still not well
understood, but growing evidence suggests there is relative of high segmental
mobility at free surface than in the bulk [23]. Because permeability is very sensitive
to free volume, gas permeability is a convenient method for tracking the aging rate
of thin films. This permeability decrease is of great significance for high flux
membranes and has been observed for asymmetric hollow fiber membranes [24-26];
e.g., Lin and Chung [26] reported that the flux (or the permeance) of polyimide
hollow fiber membranes was reduced by nearly 40% after aging for 720 hours. Due
to the complicated nature of the hollow fiber membranes, the aging mechanism was
not well recognized at that time. The integration of thin film aging data into the
analysis of high flux membrane development has become possible via some
recently developed methodology [6-20]. In this approach, thin films are first spin
coated onto a silicon wafer and then thermally annealed above Tg as free standing
films, i.e., in an unconfined environment. To date, the focus of this work have been
on polysulfone, Matrimid 5218 and poly(2,6-dimethyl-1,4-phenylene oxide)
(PPO), which are the most extensively used polymers for commercial membranes
128
[6-10, 15-18] and a series of experimental hexafluoropropane dianhydride (6FDA)
based copolyimides [11-14, 19, 20].
It is important to explore the thin film aging properties of other glassy
amorphous polymer materials, especially commercially available products of
potential interest as membrane materials, to better understand the factors that affect
aging behavior and to guide selection of new membrane materials in a more holistic
way. Polyetherimides have been extensively studied during past decades because
they potentially have attractive properties and processability [27-31]. The first
commercial polyethermide was Ultem 1000, developed by General Electric
Plastics [32]; however, this polymer has so far not been amenable to our
spin-coating techniques using common solvents. Hence, we focus on another
polyetherimide known commercially as Extem XH 1015, which has an even
higher Tg and better thermal properties, that can be successfully fabricated into
free-standing thin films. This chapter explores the aging and carbon dioxide
plasticization behavior of this new polyethermide and compares the results with
those for PSF and Matrimid 5218 from the previous work [18]. Particular attention
is devoted to the permeation response of thin films for a variety of CO2 conditions
due to the current strong interest in CO2 related separations, such as the removal of
CO2 from natural gas [33-37] and flue gases [38-41].
129
6.2.1 Aging Behavior Tracked by Gas Permeation
By knowing the glassy transition temperature of Extem as shown in Figure
6-1, the thin Extem films are heating above glass transition temperature for 15C
under N2 atmosphere in order to define the zero time point.
Figure 6-1 DSC thermograph showing the glass-transition temperature of Extem
The aging behavior of Extem thin films was monitored by observing the
change in the gas permeability of oxygen, nitrogen and methane. Carbon dioxide
was not used in the aging study because it will affect the aging process as described
later due to its high level of solubility in the polymers. Preparation of thin glassy
films requires great care and it is essential to ensure that any pinhole defects no
130
matter how small are sealed by the PDMS coating [42]. As a check on
reproducibility, several Extem thin films were prepared from different batches but
using the same protocol. The thicknesses were slightly different; however, as shown
by the O2 permeability results shown in Figure 6.2a, the data are quite reproducible.
Figure 6-2 Oxygen permeability of (a) Extem films with similar thickness and (b)
Matrimid, PSF and Extem films as a function of aging time
131
Figure 6-2b compares the aging behavior of Extem thin films, as tracked by the
O2 permeability, with that of Matrimid and PSF; the latter data were taken from
previous work [15]. After 1000 hr of aging, the O2 permeability of Matrimid and
Extem is reduced by a factor of 2 compared to their initial values, while PSF shows
somewhat less sensitivity to aging. However, for thick films only about a 10%
reduction in permeability occurs over 1000 hours [7]. At this point, we cannot
interpret the different shapes of the aging curves observed. The initial O2
permeability values at short time are all larger than those for thick films as shown in
Table 3-2. It is believed that the rapid quenching from above Tg to room
temperature leads to a somewhat higher free volume for the thin films. The initial
values of O2, N2 and CH4 permeability for 160 nm and 320 nm Extem films are
larger than that of thick films as shown in Figures 6-3a, b and c. The relatively
smaller oxygen gas molecule shows the least decline in permeability with aging,
while nitrogen and methane show larger responses. In all cases, the 156 nm film has
lower gas permeability coefficients and shows somewhat more rapid aging effects
than the 320 nm film. Figure 6-4 shows that the O2/N2 selectivity is initially lower
than the bulk value but eventually reaches and exceeds the bulk value as aging
proceeds. The thinner film has a somewhat higher selectivity than the 320 nm film.
These trends are consistent with the results observed by Huang and Paul [7] and
Kim et al. [11].
132
133
Figure 6-3 (a) Oxygen, (b) nitrogen, (c) methane permeability of Extem films with
different thickness as a function of aging time
Figure 6-4 O2/N2 selectivity of Extem films as a function of aging time
The greater aging rate of the thinner film is consistent with the proposal of
enhanced mobility at the free polymer surface [15, 23]. The initially lower
134
permeability for the thinner film is believed to be caused by aging occurring in the
first few minutes prior permeation measurements based on the modeling by Rowe
et al. [15].
6.2.2 CO2 Plasticization Pressure Curves
Plasticization of polymer membranes by CO2 is well known in the literature,
due to the high solubility of CO2 in the polymer, and can cause severe deterioration
of the CO2/light gas selectivity by increasing the permeability of all gas species,
especially at high CO2 partial pressure. There have been many reports on such
behavior based on studies using dense thick films [34, 43-47]. However, there is
growing evidence that this behavior can be quite different in thin films with
thicknesses of the order of 100 nm; the latter are believed to better reveal how high
flux commercial membranes respond. In thin films, physical aging of the glassy
polymer is much more rapid than in thick films and may compete with the
plasticization process. Zhou et al. have observed enhancement of plasticization in
thin polyimide membranes [48], while Wessling et al. found similar behavior in
composite membranes [49]. Horn and Paul [18] have reported a series of
experimental protocols for characterizing these competing effects of aging and CO2
plasticization for Matrimid, PSF and PPO thin films. They found that thin films are
more sensitive to changes in CO2 upstream pressure in permeation tests and
135
undergo more serious plasticization at high pressures. Film thickness, CO2 pressure,
aging time, exposure time and prior history are evidently important factors
influencing thin film plasticization behavior. Here, we compare the responses of
Extem to the protocols of CO2 exposure reported recently for Matrimid, PPO and
PSF. To facilitate their comparison, it is useful to understand the level of CO2
sorption in each of these polymers. As a guide for this, Figure 6-5 compares CO2
sorption isotherms for each of the polymers obtained on thick film samples. It
would be useful to have sorption data for thin films; however, obtaining such data is
a rather tedious process beyond the scope of this report. However, the sorption
curve can be obtained by using an ellipsometric technique [50]. The solubility of
CO2 in Matrimid, PPO and PSF increases as the glass transition temperature of the
polymer increases as expected from prior studies [51-53]; however, Extem deviates
somewhat from this trend. Sorption of CO2 in butyl rubber is shown for
comparison.
136
Figure 6-5 CO2 sorption isotherms for thick films at 35C: Matrimid [54], PSF [55],
PPO [56], butyl rubber [53]
Figure 6-6a shows so-called CO2 plasticization curves for thin films for Extem
plus Matrimid, PPO and PSF; to facilitate comparison, the CO2 permeability for
each polymer has been normalized by the permeability of that polymer at 2 atm. All
the films are of similar thickness (160-200 nm) and aged for 100 hr at 35 C prior to
the CO2 test in order to achieve a standardized result. The films was first exposed to
2 atm of CO2 and then the pressure was incremented by 2 atm until reaching 20 atm,
followed by increasing by 4 atm until reaching 40 atm. The films were held for 3
min (much longer than the time lag) at each pressure. The permeability data were
collected during the final 60 s. The time interval has to be precisely controlled
because the CO2 permeability is strongly affected by the previous CO2 exposure
137
history. Matrimid undergoes the greatest relative change of CO2 permeability, while
PSF shows the least. The effect of CO2 concentration on plasticization can be
presented more directly by plotting the normalized permeability versus the CO2
concentration in the polymer (thick film data) at the upstream surface as shown in
Figure 6-6b. No universal trend is observed contrary to previous studies [46, 47];
this suggests that the plasticization is related to the nature of the polymer in addition
to its sorption isotherm.
138
Figure 6-6 Normalized CO2 permeability of thin films as a function of (a) pressure
(Matrimid, PPO and PSF data are taken from the literature [18]) and (b) CO2
concentration
The observed CO2 plasticization curves for thin films are also a function of
prior aging time as shown for Extem in Figures 6-7a and b. Two thin films were
aged for 100 hr and 400 hr before plasticization evaluation. The film aged 100 hr
seems to experience greater plasticization at high pressures as made evident when
the permeability is normalized (Figure 6-7b) by using the value at 2 atm as the
standard. At low pressures (less than 15 atm), the curves for the films aged 100 hr
and 400 hr have almost the same shapes. However, the film aged 100 hr experiences
a nearly 60% increase in permeability when the pressure rises to 40 atm while the
permeability of the film aged 400 hr only increases by 20%. Thus, CO2
plasticization strongly depends on the aging time of thin films. The reduction in free
139
volume during aging may be the key issue.
Figure 6-7 (a) CO2 permeability and (b) normalized CO2 permeability as a function
of CO2 pressure for different aging times
6.2.3 CO2 Permeability Hysteresis
In order to further explore the dynamics of plasticization, a protocol similar to
140
one used previously [18, 19] was employed for thin Extem films. The protocol
consists of four parts: (1) pressurization from 2 atm to 32 atm with 10 min intervals
at each pressure; (2) hold at 32 atm for 4 hr and record the permeability change; (3)
depressurization from 32 atm to 4 atm with 10 min intervals at each pressure; (4)
hold at 4 atm overnight and record the permeability change with time. During each
pressurization stage, the permeability is measured at 2, 5 and 9 min. During each
depressurization stage, the permeability is measured at 5 and 9 min. The purpose of
this frequent measurement is to track changes over short exposure times. Three thin
films with similar thicknesses but exposed to different prior aging times (25, 100
and 150 hr) were tested using this protocol.
Figures 6-8a and b show the CO2 hysteresis curves obtained for the thin Extem
films; to make a clear comparison, the scales are the same in both figures. It is clear
that the film aged 25 hr experienced the greatest plasticization during pressurization
and hysteresis during depressurization. The extent of these effects follows the order
25 hr > 100 hr > 150 hr. The pressure where permeability is at a minimum, often
called the plasticization pressure in thick film studies, shifted from 12 atm for the
film aged for 25 hr to 20-24 atm for the film aged 150 hr. During the 10 minute
observation interval, there are noticeable increases in permeability at all pressures
for the film aged for 25 hr while such changes are only observed at 16 atm and
beyond for the film aged for 100 hr. However, for the film aged for 150 hr, such
141
changes only occur at 28 atm of CO2 and beyond. It appears that aging, or the
associated densification, stabilizes these thin films against plasticization by CO2.
Figure 6-8 CO2 permeability hysteresis curves of thin films aged (a) 25 hr, (b)
100 hr and 150 hr
During the 4 hr holding at 32 atm of CO2, as shown in Figure 6-9a, the
142
permeability of the film aged for 25 hr increases significantly but eventually
decreases with time. The film aged for 100 hr showed an even larger increase in
permeability during this period before declining. The film aged for 150 hr showed
the least increase during this time scale with no decline over the time frame studied.
We believe these effects are due to the competing dynamics of plasticization and
physical aging. This will become clearer from observations over a longer time of
CO2 exposure as discussed later.
143
Figure 6-9 CO2 permeability as a function of time at (a) 32 atm (after increase CO2
pressure)and (b) 4 atm (after decrease CO2 pressure) during hysteresis testing
The response of the Extem thin films to depressurization is notably different
from that of Matrimid and PPO studied previously [18]. The permeability keeps
increasing and reaches the maximum point at 4 atm. This behavior does not mean
that the film undergoes greater plasticization at lower pressures but a longer time
144
scale is needed for Extem to respond to the decreased CO2 content or to relax. With
sufficient relaxation time, as shown later in Figure 6-9b, the films held at 4 atm of
CO2 overnight show a monotonic decline of permeability.
6.2.4 CO2 Permeation Behavior for Short Exposure Times
The previous discussions about CO2 permeation behavior are all based on
complicated protocols, where the CO2 pressure and exposure time are changed
frequently. In this section, Extem thin films are exposed to 8, 16, 24 and 32 atm of
CO2 for 2 hr each. Matrimid and PSF data using the same procedure [18] are also
included in Figures 6-10a and b for comparison. As discussed in the previous study
[18], Matrimid begins increasing in permeability upon each change in pressure,
while PSF shown an opposite trend. Extem behaves more or less the same as
Matrimid. Under 8 atm of CO2, although the pressure is lower than the
plasticization pressure, the Extem thin films already experience plasticization.
145
Figure 6-10 (a) CO2 permeability and (b) normalized CO2 permeability in 2 hr CO2
exposure at programming higher pressures
146
6.2.5 CO2 Permeation Behavior over Long Exposure Times
The aforementioned experiments represent relatively short periods of exposure
to a CO2 feed while industrial membranes may be exposed over numerous years.
Thus, it is important to explore longer term effects of CO2 plasticization on these
thin films. Three Extem thin films aged 200 hr were exposed to 8, 16 and 32 atm of
CO2 for roughly 200 hr as shown in Figures 6-11a and b. As might be expected, the
CO2 permeability of each film increases with time at the beginning; however, as
reported previously, the permeability reaches a maximum and then declines. At 32
atm, the permeability occurs within 2 hr and reaches a value that is 50% greater than
the initial value. At 8 atm, the film takes 100 hr to reach the maximum, and this
maximum value is only 10% higher than the initial permeability. The film exposed
to 16 atm of CO2 shows intermediate behavior. As discussed in elsewhere [18],
physical aging appears to be the dominate effect after the film has reached the
maximum permeability. There is some reason to believe from these long term
exposure experiments that higher pressures of CO2 may accelerate the physical
aging process.
147
Figure 6-11 (a) CO2 permeability and (b) normalized CO2 permeability during long
time CO2 exposure at different pressures
The long time exposure effects for Extem are compared with that of Matrimid
and PSF [18] in Figures 6-12a a~b and Figures 6-13a~b. At 8 atm of CO2, Matrimid
shows the greatest relative maximum, while PSF shows a slight, but broad,
148
turnover. The exposure time for Extem to reach the maximum appears to be
longer than that of Matrimid. At 32 atm of CO2, Extem experiences the highest
relative change in permeability at an exposure time of 2 hr. The difference between
Matrimid and PSF has been attributed to the differences in CO2 sorption. However,
the data for Extem does not appear to fit this expectation, suggesting that these
effects are more complex than simply the amount of CO2 sorbed by the polymer.
However, one must remember that this is based on thick film data. More
information about aging and plasticization behavior of other polymers may be
needed to establish any universal rules.
149
function of exposure time at 8 atm for different polymer films
150
function of exposure time at 32 atm for different polymer films
Summary
The aging properties and CO2 plasticization behavior of a new polyetherimide
(Extem XH 1015) have been systematically explored using different protocols
developed in a previous paper from this laboratory [18]. The aging properties
follow the same general trend as reported for a few other polymers of interest,
including polysulfone and the polyimide known as Matrimid. Based on available
data for CO2 sorption in thick films made from these polymers, it appears that the
level of CO2 sorption itself may not be the unifying factor to explain the different
response to the CO2 exposure observed for these polymers. For a particular polymer,
CO2 plasticization is a function of film thickness, CO2 pressure, exposure time,
151
aging time and prior history. Indeed, one might speculate that the fractional free
volume and its change with time and CO2 exposure may be an important factor in
this picture.
152
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160
CHAPTER 7 Gas Permeability Comparison of Extem
XH1015 with Polysulfone and Ultem via Molecular
Simulation
J. Xia, S. Liu, P.K. Pallathadka, M.L. Chng, T.-S. Chung, Structural determination of
Extem XH 1015 and its gas permeability comparison with polysulfone and ultem via
molecular simulation, Industrial & Engineering Chemistry Research, 49 (2010)
12014-12021
161
Abstract
Extem XH 1015 is a new brand of polyetherimide with good thermal,
mechanical properties and processability. The gas permeability of this new polymer
is reported for the first time. Polysulfone (PSU) and Ultem are employed as
reference samples for the elucidation of permeability and selectivity differences
among them because of their structural similarities. In addition to qualitative
comparison of chain rigidity and packing with gas transport properties,
computational simulations powered by Material Studio are performed at a
molecular level to quantitatively investigate the relationship between the fractional
accessible volume (FAV) and gas permeability. The FAV differences among these
polymers increase with an increase in gas molecules diameters; thus these polymers
have similar permeability for small gas molecules but diverse for large gas
molecules. Their selectivity differences are also discussed in terms of FAV ratio.
The FAV concept is proved to be more effective than free volume to analyse and
predict gas separation performance.
162
7.1 Introduction
Throughout history, human beings have witnessed many evolutions involving
materials. The emergence of engineered plastics is of interest. Polyimide is one of
these high performance engineering plastics aiming at replacing metals as well as
targeting other specialty applications such as electronics, automotives, and
membranes. However, not all the polyimide materials meet industrial specifications
because of their poor processability rendered by high chain rigidity and high glass
transition temperatures. One of the exceptions is PEI (polyetherimide), which is a
particular class of polyimides that not only retains high temperature characteristics
but also possesses good melt processability. It has balanced physicochemical
properties between performance and practicability due to the introduction of ether
group. One of the commercialized PEI was developed by GE (general electric)
Plastic in 1986 under the trademark of Ultem. It was synthesized from bisphenol-A
dianhydride (BPADA) and meta-phenylene diamine (MPD) through condensation
polymerization [1]. This polyetherimide has already been employed in many
applications, such as healthcare applications, pharmaceuticals and membrane
separations. Gas separation membrane made from Ultem in Pauls group [2] has
shown impressively high selectivity for many gas pairs, especially for
helium/methane.
163
In recent years, Extem XH1015, a new brand of polyetherimide, was
developed by GE, and has been commercialized in Europe since 2007. This so
called amorphous thermoplastic polymer offers a higher Tg (267C), exceptional
dimensional stability, high strength, stiffness, and creep resistance at elevated
temperatures, outstanding flame, smoke and low smoke-toxicity performance
without additives. Even though the Extem XH resin is not the strongest material at
room temperature, it outperforms many other high-performance amorphous and
semi-crystalline thermoplastics at temperatures exceeding 240C by remaining
most of its tensile strength and creep resistance [3]. Unlike other semi-crystalline
thermoplastic polyimides, this fully amorphous Extem XH does not need any post
heat treatment to achieve its desired properties.
Based on our previous understanding on polyetherimide [2], this new
amorphous material may have potential to be a membrane material due to its higher
Tg as compared to Ultem. However, the dense Extem membrane does not show
impressive gas separation performance. Further endeavor is hindered by the lack of
information on its chemical structure to explain its structure relationship with gas
permeability and to explore methodologies for chemical and physical modifications
to enhance its application potentials. A bundle of patents [4-8] filed by GE provided
few clues on this new PEI, but the detailed structure under the trademark of Extem
had never been released. In appendix A, the chemical structure of Extem XH1015
164
has been determined by using NMR, elemental analysis and FTIR.
Interestingly, Extems main chemical repeating unit is quite similar to another
grade of commercial PEI, named Ultem XH6050, of which the chemical structure
also consists of a sulfone group [9]. This so-called PEIS (polyetherimide sulfone)
combines the desired properties of polyetherimide and polysulfone into a single
resin, which include good processability, high Tg and good thermal stability at high
temperatures. The good melt processability may be derived from the unique
characteristics of polyetherimde and polysulfone. Gallucci and Malinoski [10]
reported that the end group of PEIS plays an important role on its Tg and thermal
stability. PEIS, which has the same structure with Ultem XH6050, has a higher Tg
(258C) by employing more anhydride as the end groups. This suggests that the
same strategy may also be employed to improve the Tg of Extem XH1015. Their
similar physical properties [3] indirectly support our hypothesis.
Since polysulfone (PSU) and Ultem contain part of the repeating unit in Extem as
illustrated in Figure 7-1, the objectives of this chapter are to correlate its gas
permeation properties with its chemical structure via both experiments and
molecular simulation, and to further investigate its potential as a material for gas
separation.
165
Figure 7-1 Chemical structures of PSU, Extem and Ultem
7.2.1 Chain Morphology Comparison
Figure 7-2 Chain morphologies of PSU, Extem and Ultem with 5 repeat units
Figure 7-2 shows the single chain morphologies of PSU, Extem and Ultem
containing 5 repeating units at the completely extended state. Although the

166
morphologies are far from the real conformation in our membranes, it is still
valuable for the qualitative discussion to correlate the membrane gas permeation
performance with their chemical structures. As we can see in this figure, Ultem,
being the most rigid polymer, takes a much extended chain conformation; while
PSU, the softest one, exhibits a zigzag like morphology. Usually, an increase in
chain stiffness is accompanied with a decrease in segmental mobility. As a result,
from PSU, Extem to Ultem, the thermal motions generating transient gaps for
penetrants to diffuse decrease. These calculated chain morphologies correlate well
with their gas selectivity as shown in Table 7-1.
Table 7-1 Gas permeation performance of flat dense PSU, Extem and Ultem
membranes
a
1 Barrer = 11010 cm3(STP) cm/cm2 s cmHg = 7.50051018 m2 s1 Pa1;
b
Density simulated from Material Studio;
c
FFV Calculated from Bondi-Park & Pauls method;
d
FFV calculated from Material Studio.
The sequence of chain rigidity in these polymers can also be elucidated from
their monomers. PSU and Extem both have bisphenol A and diamino diphenyl
sulfone (DDS) moieties. The additional heterocyclic imide group in Extem induces
167
a planar and relatively larger ring in the backbone, which increases the chain
rigidity. The introduction of a heterocyclic imide group also enhances the
inter-chain attractions. As shown in Figure 7-3, where two Extem polymer chains
are constructed at fully extended state, two heterocyclic imide rings are partially
aligned parallel to each other to minimize the total energy. This inter-chain
attraction effect increases the chain packing efficiency, thus leading to a lower
permeability. Ultem also has the same phenomenon, while PSU polymer chains
could not be aligned in parallel, which correlates well with its high permeability.
Although the discussion is only valid in the ideal case, the polymer chain packing
will still follow the principle of minimum total potential energy in the real materials.
Comparing Extem with Ultem, the only difference is that the meta-phenylene
diamine (MPD) moiety in Ultem is replaced by DDS in Extem. Since the DDS
structure can reduce the effective chain packing due to tetrahedral configuration of
the -SO2- group, Extem has a higher permeability and a lower selectivity than
Ultem.
168
Figure 7-3 Morphology of two polymer chains with 5 repeat units for PSU,
Extem and Ultem
7.2.2 Molecular Simulation
The FFV values calculated by both the Bondi-Park & Paul method [11] and
Material studio were listed in Table 7-1 in order to compare their gas separation
performance quantitatively. PSU has the largest FFV, which correlates well with
experimental data of the highest permeability. However, there is a contradiction
when it comes to Extem and Ultem. The FFV value of Extem calculated by the
Bondi-Park & Paul method is smaller than that of Ultem, while the permeability of
Extem is much larger than that of Ultem. Obviously, the FFV concept alone cannot
interpret this discrepancy because FFV just gives a sum of the total free volume
with no differentiation for different penetrants with different dimensions. In order to
169
explain this contradiction, the fractional accessible volume (FAV) distributions of
PSU, Extem and Ultem, as well as their relative FAV values raised by Chang et al.
[12] in terms of PSU/Ultem and Extem/Ultem were calculated and listed in Figure
7-4. In our case, the relative FAV values were defined, respectively, as follows:
FAV ( PSU ) FAV (Ultem )

100% (7-1)
FAV (Ultem )
and
FAV ( Extem ) FAV (Ultem )

100% (7-2)
FAV (Ultem )
Figure 7-4 Fractional accessible volumes and relative FAV values of PSU, Extem
and Ultem, probed with different diameters
The selection of the horizontal axis values is based on the kinetic diameter of
the probe gas molecule, as shown in Table 7-2 for easy interpretation with
permeation data.
170
Table 7-2 Kinetic diameters of various gases
For one particular gas, three FAV values were calculated from these three
polymers. It can be seen that the FAV of PSU is always the largest, which correlates
well with its highest permeability of all gases as presented in Table 7-1. While the
FAV values of Ultem are always the smallest, correlating well with its lowest gas
permeability. Furthermore, for all the three polymers, gas permeability and the
reciprocal of FAV follow linear relationships for relatively larger gas molecules,
especially for methane and nitrogen as shown in Figure 7-5, even though their
polymer structures are different. In Table 7-1, if can be seen that when the gas
molecule diameter is small, the difference in their gas permeability is small, while
when the gas diameter increases, this difference increases. For example, the helium
permeability coefficients of PSU, Extem, and Ultem are 13, 11.1 and 9.4 barrers
with a ratio of 1.38:1.18:1, while the methane permeability coefficients become
0.25, 0.13 and 0.036 barrers with a ratio of 6.94:3.61:1. These phenomena can be
well explained using the relative FAV concept. As plotted in Figure 7-4, the relative
FAV values of PSU/Ultem and Extem/Ultem increase when the probe diameter
increases. In other words, the FAV difference between PSU and Ultem becomes
larger when the probe diameter increases. This indicates that the fractional
171
accessible volume is a more precise tool in analyzing the gas permeability than the
total free volume.
Figure 7-5 Correlation between gas permeability and 1/FAV
The gas selectivity of polymer dense membranes shows a good correlation with
the FAV ratio, which was defined for Extem and Ultem, as follows:
FAV ( Extem )
100% (7-3)
FAV ( PSU )
and
FAV (Ultem )
100% (7-4)
FAV ( PSU )
As shown in Figure 7-6, the FAV ratio of Ultem/PSU is about 76% for helium, while
it is only 63% for methane. This means, using PSU as a reference, that the fractional
accessible volume for both helium and methane transport in Ultem is less than in
PSU. However, the decrease of FAV for methane is more severe than that for helium.
172
Thus, the helium/methane selectivity increases from 56 for PSU to 261 for Ultem.
The same approach could be used to explain the helium/methane selectivity
increase in the Extem membrane. Another method is to investigate the slope of a
straight line connecting any two data points of interest on the FAV curve. For any
gas pair in one particular polymer, if the slope of the line between the selected two
data points is negative, the selectivity of this gas pair for this particular polymer is
higher than the reference polymer. For example, if helium and methane are chosen
in the Ultem/PSU FAV ratio curve, the slope of line between these two points is
definitely negative. Therefore, the selectivity of helium/methane is better in Ultem
than in PSU. When comparing the gas selectivity of more than two polymers, this
approach is still validate by just choosing one reference polymer. For example, if
there are two straight lines linking helium and methane in the Ultem/PSU and
Extem/PSU FAV ratio curves, the absolute value of the slope for Ultem/PSU is
obviously larger than that for Extem/PSU. This demonstrates that the
helium/methane selectivity difference between PSU (56) and Ultem (261) is larger
than that between PSU (56) and Extem (85). This method could explain other gas
pairs as well, like O2/N2. The absolute value of the slope between O2 and N2 in the
Extem/PSU FAV ratio curve is smaller than that in Ultem/PSU. This correlates well
with their gas selectivity difference between PSU (5.6)/Extem (6.2) and PSU
(5.6)/Ultem (8.0), respectively.
173
Figure 7-6 FAV ratios of Extem/PSU and Ultem/PSU probed by different diameters
Summary
Gas permeability of Extem dense membranes was reported for the first time.
Due to the structural similarities, PSU and Ultem are used for comparison of
fractional free volume (FFV), fractional accessible volume (FAV), gas
permeability and selectivity. The effect of different monomer structure in their gas
separation performance is also discussed in detail. Computational simulation
powered by Material Studio, especially the FAV value simulation was shown to be
a more accurate method to analyse and predict gas separation performance.
174
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176
CHAPTER 8 Conclusions and Recommendations
8.1 Conclusions
Gas separation membranes have been evaluated for removing CO2 from gas
mixtures, mainly CO2/H2 and CO2/N2. This thesis shows that blending poly
(ethylene glycol) (PEG) and its derivatives into organic-inorganic membranes
(OIMs) is an efficient approach to increase the ethylene oxide content and
decrease the crystallinity of PEG. Thus, high CO2 permeability and CO2/light gas
selectivity could be achieved simultaneously. By monitoring the gas permeability
and selectivity of glassy thin films, accelerated physical aging and its competition
with CO2 plasticization was observed. This finding greatly enhances our
understanding on the flux decrease of hollow fiber modules along with the time.
The preliminary results obtained from simulation works also reveal a possibility
of replacing experiments by performing computational simulations.
8.1.1 Permeability and Selectivity Enhancement by Blending PEG and its
Derivatives
Organic-inorganic membranes (OIMs) based on PEG and siloxane is a great
matrix for modification with low molecular weight PEG and its derivatives.
177
Within the confined space, PEG and its derivatives behave like a liquid in a stable
state. The overall permeability is greatly enhanced by the extraordinary increase
of CO2 diffusivity caused by addition of PEG. The selectivity is improved slightly
by adding more ethylene oxide groups, in other words, by increasing the content
of blended PEG. The end groups of PEG derivatives also play an important role to
determine the extent of permeability enhancement. Hydrogen bondings formed
between hydroxyl groups of PEG prevent the further increase of gas diffusivity.
8.1.2 Permeability Enhancement by Grafting PEG-azide on the Backbone
of OIMs
The crystallization tendency of PEG is greatly depressed after PEG-azide is
partially immobilized on the backbone of OIMs. In addition, a high amount of
chain ends and packing defects would possibly be created by this chemical
grafting. Therefore, the diffusivity of gases increases tremendously following this
modification.
8.1.3 Temperature Effect on Gas Permeability and Selectivity
A significant permeability jump is observed when the testing temperature
surpasses the melting point of PEG or PEG-azide. Both diffusivity and solubility
178
are increased due to the melt of crystals. The crystals are impermeable because gas
diffusivity and solubility in these domains are theoretically zero. When crystals
melt, there is more material through which permeation can occur and the torture
path around the crystal is eliminated. Thus permeability takes a large jump.
8.1.4 Physical Aging and Plasticization on Polymeric Thin Films
For the films with thickness in nanometer range, an accelerated physical
aging is observed for several common glassy polymers. This phenomenon could
be attributed to the higher mobility of surface compared to the bulk or the
diffusion of free volumes from bulk to the surface. However, these two
explanations have not been proved by experimental methods till now. For a
particular polymer, CO2 plasticization is a function of film thickness, CO2 pressure,
exposure time, aging time and prior history. The aging rate increases when the film
becomes thinner. The higher the CO2 pressure imposed on the film, the faster the
plasticization happens. With longer aging time prior to plasticization experiment,
the film is harder to be plasticized. Indeed, one might speculate that the fractional
free volume and its change with time and CO2 exposure may be an important factor
in this picture. With thinner films,
179
8.2 Recommendations
8.2.1 PEG Based Organic-Inorganic Membranes
In this dissertation, a series of poly (ethylene glycol) based organic-inorganic
membranes have been developed, and the results appears quite promising.
However, the effect of water vapour, which is also one of the major components in
the flue gas, has not been explored on this preliminary investigation. In fact, these
PEG based membranes may swell due to the existence of water vapour. Several
single testings containing small amount of water vapor have been performed.
However, no conclusion could be reached at this time. Further works should
explore more towards the effect of water vapour on these membranes.
All the OIMs were tested in thick film form. Therefore, it is a challenge to
apply these materials as the selective dense layer of thin film composite
membranes. Some preliminary efforts to coat these materials on polysulfone
hollow fibers have been made. However, more work in this area will be conducted
to convert these OIMs into high flux composite membranes. Severe intrusion of
coating solution into ploysulfone support made these membranes less permeable.
Complicated preparation process of these OIMs and their shrinkage during
crosslinking process may be other reasons preventing these composite membranes
to be defect-free. The hydrolysis and condensation time may be the key to tailor
180
the viscosity of the coating solution.
8.2.2 Physical Aging and Plasticization Monitored by Gas Permeability
All the works on physical aging and CO2 plasticization are now based on pure
gas permeation testing. Preliminary result shows that aging is a function of film
thickness, CO2 pressure, prior thermal and CO2 exposure history. The mechanism
and dynamic of physical aging of polymers are not fully understood at current
stage. It is believed that glassy transition temperature of thin films plays an
important role to determine their aging characteristics from a review of basic
polymer physics. Lots of literatures show a change of glass transition temperature
when the thickness of films deceases into nano-meter range. However, there is no
agreement till now.
Diffusivity and solubility are the two basic factors to determine the gas
transport properties of a membrane. There is no mature technique to monitor the
diffusivity for thin film right now. However, elliposometry had been proved as a
pioneer technique to measure the solubility of gases in thin film. By knowing
solubility, diffusivity can be obtained by a back calculation. This information can
be extremely useful to understand the plasticization phenomenon in thin film.
Furthermore, it will be very interesting if the work could be extended to mixed
181
gases monitoring. Some transport properties of thin film, like solubility and
diffusivity, already show differences with that of thick film, so the mixed gases
permeation experiments may have different behaviours as well. In reality, the
thickness of the dense selective layer of a gas separation membrane is only few
nano-meters. Thus, the mixed gases experiments made on thin film will be much
more meaningful to lead a discussion.
182
Appendix A: Structure determination of Extem XH 1015
The structure of Extem XH 1015 was unknown when it was purchased
from supplier since it was newly commercialized. In order to make proper
discussion on work using this material, the structure of this polymer was
determined by using NMR, elemental analysis and FT-IR. This structure was
determined in 2010 and verified by their company one year later.
Results
The strategy of determining the chemical structure Extem XH 1015 is to combine
the information from patents and experiments. NMR, especially 2-D NMR was
used to determine the protons position and their relationship with carbon. The 1H
NMR and 13C NMR spectra of Extem XH 1015 are illustrated in Figure A-1 and
Figure A-2, respectively.
Figure A-1 H-NMR spectrum of Extem XH1015

183
Figure A-2 C-NMR spectrum of Extem XH1015
The 2D-NMR spectra used to assign each carbon and proton in the aromatic
region are given in Figure A-3 and Figure A-4.
Figure A-3 COSY spectrum of Extem XH1015
184
Figure A-4 HETCOR spectrum of Extem XH1015
In addition to NMR spectra and FTIR-ATR shown in Figure A-5, the elemental
analysis results of this polyetherimide sulfone shown in Table A-1 also generally
agree with the theoretical values for the proposed structure. Very minor differences
are found due to experimental error and/or different element compositions of the
polymer end group. As discussed previously, dianhydrate may be used to cap the
polymer chain. As a result, the overall nitrogen and sulfur content is a little bit lower
than the theoretical value.
185
Figure A-5 The FTIR-ATR spectrum of Extem XH1015 film
Table A-1 Experimental and theoretical elemental analysis
The aliphatic parts of 1H- and 13

C-NMR spectra of Extem can be completely
interpreted with the aid of the 1H-13C-HETCOR spectrum (not shown here
because its position is too far away from the aromatic region). The adsorption of
C-12 carbon at 30.9 ppm of the 13C-NMR spectrum correlates well with a very
sharp singlet of H-a protons at 1.64ppm of the 1H-NMR spectrum, revealing the
existence of methyl group. C-13 at 42.5 ppm is also in the aliphatic region due to a
relative low chemical shift compared to these carbons in the aromatic region
186
(110-170ppm). However, the 1H-13C-HETCOR spectrum does not show any proton
connected to this carbon. The above evidences all strongly support a 2,2-
substituted propane structure in the Extems backbone.
Although the area integration curve of all proton peaks is not shown in Figure A-1,
the peak area ratio of a~h protons could be determined roughly to be 3:2:1:2:1:2:1:2,
which is well coincident with the theoretical protons ratio based on the chemical
structure of Extem. Fortunately, aromatic protons, except H-g, all belong to the AX
two spin system [1]. Each peak of these protons is observed as a small doublet that
is split by the proton nearby. The 1H1H correlation (COSY) performed in CDCl3 is
shown in Figure A-3, revealing that H-b (7.04-7.06 ppm) is split by H-d (7.28-7.30
ppm) through a 3-bond coupling. So do H-h (8.13-8.15 ppm) and H-f (7.72-7.74
ppm) pair, as well as H-e (7.63-7.65 ppm) and H-c (7.15-7.17 ppm) pair. The H-g at
7.18 ppm is assigned as an isolated proton because of its absence from the COSY
spectrum, although it is overlapped by H-f.
13
Figure A-2 shows the signal assignment for a C NMR spectrum with 1H noise
decoupled during acquisition. These carbon atoms at the high frequency are mainly
attached to heteroatoms, making them valuable in the determination of monomers,
especially diamino monomer. Carbon atom C-1 (165.9 ppm) is assigned to the
imide carbonyl group. C-5 (164.2 ppm) and C-8 (152.7 ppm) constituting the
187
BPADA ether segment are assigned due to the direct connection to the oxygen atom.
A similar carbon chemical shift is also found for C-17 (147.5 ppm) in the
polysulfone 13C-NMR spectrum [2]. The assignment of each peak marked in Figure
3 is assisted by the correlations shown in 1H-1H COSY (Figure A-3) and 1H-13C
HETCOR (Figure A-4) spectra to fit the structure of polyetherimide sulfone.
In the case of FTIR-ATR spectra as shown in Figure A-5, bands at around 1781 cm-1
(attributed to C=O asymmetric stretch of imide groups), 1717cm-1 (attributed to
C=O symmetric stretch of imide groups) and 1360 (attributed to C-N stretch of
imide groups) are characteristic imide peaks as indicated in Shao et al.s work [3].
Although parts of the band at 1320 cm-1 (attributed to -SO2- asymmetric stretch) are
overlapped by strong adsorption of the imide group at 1360cm-1, the existence of
sulfone group can still be proved by the strong peak at 1150cm-1 (attributed to -SO2-
symmetric stretch ) [4].
References
[1] Friebolin, H. Basic one and two dimensional NMR spectroscopy 3rd ed.;
Weinheim: New York, 1998.
[2] Pham, Q.; Ptiaud, R. Proton and carbon NMR spectra of polymers 5th ed.;
Wiley: New York, 2003.

188
[3] Shao, L.; Chung, T.S.; Goh, S.; Pramoda, K. Transport properties of
cross-linked polyimide membranes induced by different generations of
diaminobutane (DAB) dendrimers. J. Membr. Sci. 2004, 238, 153.
[4] Bolong, N.; Ismail, A.F.; Salim, M.R.; Rana, D.; Matsuura, T. Development and
characterization of novel charged surface modification macromolecule to
polyethersulfone hollow fiber membrane with polyvinylpyrrolidone and water.
J. Membr. Sci. 2009, 331, 40.
189

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POLYMERIC GAS SEPARATION MEMBRANES FOR

CARBON DIOXIDE REMOVAL

XIA JIAN ZHONG

(B. S., Peking University, P. R. China)

A THESIS SUBMITTED FOR THE DEGREE OF

NUS Graduate School for Integrative Sciences and

NATIONAL UNIVERSITY OF SINGAPORE

I wish to take this opportunity to express my sincere appreciation to all the

contributors during my years in the National University of Singapore and University

of Texas at Austin. First of all, I am especially grateful to my supervisors, Professor

scholarship offered by NUS Graduate School for Integrative Sciences and

Engineering. They provide me lots of chance to attend international conferences,

University of Singapore and people in Prof. Pauls group in University of Texas at

TABLE OF CONTENTS ........................................................................................iii

LIST OF TABLES .................................................................................................xii

LIST OF FIGURES .............................................................................................. xiv

1.1 Membrane Technology for Gas Separations ...................................... 2

1.2 History of Gas Separation Membranes ............................................... 3

1.3 Applications Based on Gas Separation Membranes ........................... 4

1.3.1 Hydrogen recovery ............................................................................. 5

1.3.2 Nitrogen Enrichment .......................................................................... 7

1.3.3 Recovery of Organic Vapor ................................................................ 7

1.3.4 Carbon Dioxide Capture ..................................................................... 8

1.4 Materials for Gas Separation Membranes ........................................ 11

CHAPTER 2 Background and Approaches ........................................................... 22

2.2 Solubility .......................................................................................... 24

2.3 Fractional Free volume ..................................................................... 26

2.4 Gas Transport in Rubbery Polymers ................................................ 27

2.5 Gas Transport in Glassy Polymers ................................................... 28

2.6 Effect of Temperature ....................................................................... 29

CHAPTER 3 Materials and Experimental Methods .............................................. 33

3.1 Materials ........................................................................................... 33

3.2 Preparation of Dense Membranes..................................................... 35

3.2.1 Preparation of Glassy Thick Membranes ......................................... 35

3.2.2 Preparation of Organic-Inorganic Membranes (OIMs) .................... 36

3.3 Preparation of Polymeric Thin Films ............................................... 39

3.4 Characterization of Physicochemical Properties .............................. 41

3.4.1 Measurement of Gel Content ............................................................ 41

3.4.2 Fourier Transform Infrared Spectrometer (FTIR) ............................ 42

3.4.3 Transmission Electron Microscopy (TEM) ...................................... 42

3.4.4 Thermogravimetric Analysis (TGA) ................................................ 42

3.4.6 X-ray Photoelectron Spectrometer (XPS) ........................................ 43

3.4.7 Elemental Analysis ........................................................................... 43

3.4.8 Nuclear Magnetic Resonance (NMR) .............................................. 44

3.4.9 Simulation Based on Molecular Dynamic ........................................ 44

3.4.10 Variable Angle Spectroscopic Ellipsometer ..................................... 46

3.5 Characterization of Gas Transport Properties .................................. 47

3.5.1 Pure Gas Permeation Tests ............................................................... 47

3.5.2 Mixed Gas Permeation Tests ............................................................ 48

3.5.3 Pure Gas Sorption Tests ................................................................... 48

CHAPTER 4 Liquid-like Polyethylene Glycol Supported in the Organic-inorganic

Matrix for CO2 Removal .................................................................. 53

4.1 Introduction ...................................................................................... 55

4.2 Results and Discussion ..................................................................... 60

4.2.1 Basic Physicochemical Properties .................................................... 60

4.2.2 XRD Characterization ...................................................................... 67

4.2.5 Effect of Testing Temperature .......................................................... 77

4.2.5 Effect of PEGs Molecular Weights ................................................. 81

Performance of Polyethylene Glycol Based Membranes ................. 96

5.1 Introduction ...................................................................................... 98

5.2 Results and Discussion ..................................................................... 99

5.2.1 Basic Physicochemical Properties .................................................... 99

5.2.3 Thermal Properties of GPA1100 Series ......................................... 105