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Highly permeable membrane materials for CO2 capture

Article  in  Journal of Materials Chemistry A · October 2013

DOI: 10.1039/C3TA13066E

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Highly permeable membrane materials for CO2 capture†

Cite this: J. Mater. Chem. A, 2013, 1,
Qiang Fu,ab Andri Halim,ab Jinguk Kim,ab Joel M. P. Scofield,ab Paul A. Gurr,ab
13769 Sandra E. Kentisha and Greg G. Qiao*ab

Received 5th August 2013
Accepted 13th September 2013
DOI: 10.1039/c3ta13066e
www.rsc.org/MaterialsA
The release of large quantities of CO2 into the atmosphere has been linked to global warming and climate
anomalies. Membrane processes offer a potentially viable energy-saving alternative for CO2 capture in
comparison with conventional technologies such as amine absorption. However, gas separation
membranes that are currently available have insufficiently high permeance (flux) for large scale
applications such as the treatment of high volume flue gas with low concentration of CO2. Here we
demonstrate a class of thin film composite (TFC) membranes, consisting of a high molecular weight
amorphous poly(ethylene oxide)/poly(ether-block-amide) (HMA-PEO/Pebax
2533) selective layer and a
highly permeable polydimethylsiloxane (PDMS) intermediate layer which was pre-coated onto a
polyacrylonitrile (PAN) microporous substrate. In contrast to the performance of conventional materials,
the selective layer of TFC membranes shows super-permeable characteristics and outstanding CO2
separation performance. This unprecedented result arises from the introduction of HMA-PEOs into the
Pebax
2533 matrix, leading to high CO2 permeability and flux. These results provide an encouraging
direction to further develop TFC membranes for efficient CO2 capture processes.

1. Introduction Polyethylene oxide (PEO) has attracted much attention in

The use of polymeric membranes has been considered as an
effective tool to separate CO2 from a mixture of gases due to
their adaptability, operational simplicity, low energy
consumption, low capital cost and environmental friendliness
when compared to conventional separation methods such as
absorption with amine solutions.1,2 However, current commer-
cial membranes are not competitive for this application as their
permeance (ux) for CO2 is low.3 The development of novel thin
lm composite (TFC) membranes has gained much attention
due to their potential for increased ux and hence higher energy
efficiency for gas separation.3–10 In order to manufacture defect-
free membranes, the TFC membrane generally should have a
thin (<300 nm) polydimethylsiloxane (PDMS) lm as an inter-
mediate layer between the substrate and the selective layer. This
concept was developed by Lundy11 and demonstrated in
previous studies.3,4,12 The highly permeable PDMS intermediate
layer works as a protective coating which prevents the pene-
tration of diluted polymer solution into the porous structure
and renders the entire membrane surface smoother.4,6
a
Cooperative Research Centre for Greenhouse Gas Technologies, Department of
Chemical and Biomolecular Engineering, The University of Melbourne, VIC 3010,
Australia. E-mail: gregghq@unimelb.edu.au; Fax: +61 3 8344 4153; Tel: +61 3 8344
8665
b
Polymer Science Group, Department of Chemical and Biomolecular Engineering, The
University of Melbourne, VIC 3010, Australia
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c3ta13066e
CO2 separation membranes as the ethylene oxide (EO) unit can
exhibit favorable interactions with CO2 compared to light gases,
i.e. H2, He, N2 and CH4.13–18 Recent studies have been focused on
a facile approach to enhance the CO2 separation performance
by blending PEO polymers into poly(ether-block-amide)
(Pebax) copolymers.19–21 Pebax is a thermoplastic elastomer
combining linear chains of rigid polyamide (PA) segments
interspaced with exible polyether (PE) segments.22–24 It is
believed that the hard PA block provides the mechanical
strength, whereas gas transport occurs primarily through the
so PE block.20,21,25 The blend membranes of Pebax 1657 and
gra copolymers containing PEO segments exhibit high CO2
permeability and high CO2/N2 and CO2/H2 selectivity.26
Blending PEO200 with Pebax 1657 nearly doubles the CO2
permeability.20,21 However, the PEO additives have been limited
to low molecular weight PEOs (ca. Mn < 300 Da) as high
molecular weight PEOs cause crystallinity, which leads to a
decrease of free volume and lower permeability.19 Yave and Car
blended the poly(ethylene oxide)-poly(butylene terephthalate)
(PBT-PEO) copolymer with low molecular weight PEO200, and
they observed an increase in CO2 permeability (from 150 to 750
Barrers) without loss of selectivity.7 Although high molecular
weight amorphous PEO (HMA-PEO) is expected to signicantly
increase the proportion of EO moieties,27 there is no existing
method to synthesize HMA-PEOs and therefore there is no study
on the effects of blending HMA-PEO into membrane systems.
In the present work, we introduce a new approach of
blending high molecular weight amorphous PEO with high EO
moieties into the existing membrane system. Pebax 2533,

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Journal of Materials Chemistry A
which is composed of 20% amide groups and 80% ether link-
ages (Scheme 1), was selected as the base polymer for the
membrane matrix. A multi-block HMA-PEO copolymer is
synthesized and the multi PEO blocks are interspaced with a
specially designed terephthalic spacer, which reduces the PEO
crystallinity. The incorporation of HMA-PEO into the Pebax
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matrix to form the selective layer displayed unprecedented CO2
separation ability (permeance >900 GPU, 1 GPU ¼ 106 cm3
(STP) cm2 s1 cm Hg1). In addition, we also found that this
blending method successfully suppresses any possible crystal-
linity caused by HMA-PEO copolymers. The synthesized HMA-
PEOs are fully characterized by gel permeation chromatography
(GPC) and proton magnetic resonance spectroscopy (1H NMR).
Pebax/HMA-PEO TFC blend membranes are characterized by
scanning electron microscopy (SEM), X-ray photoelectron
spectroscopy (XPS) and X-ray diffraction (XRD) measurements.
Calculations show that the selective layer presented
outstanding CO2 separation properties with a CO2 permeability
of 780 Barrer, a CO2 permeance of 2000 GPU and a CO2/N2
selectivity of 40. These results surpassed the most recent upper
bounds and make this simple HMA-PEO copolymer an attrac-
tive additive for advanced CO2 separation membranes.
2. Experimental
2.1 Materials
1,3,5-Benzenetricarbonyl trichloride (TMC, 98%), terephthaloyl
chloride (TCL, >99%), and poly(ethylene oxide) (PEO400, Mn ¼
400 Da and PEO1k, Mn ¼ 1.0 kDa) were purchased from Sigma-
Aldrich and used as received. Aminopropyl terminated polydi-
methylsiloxane (NH2–PDMS–NH2, Mn ¼ 5.0 kDa) was purchased
from Gelest Inc. and used as received. Deuterated chloroform
(CDCl3, 99.9%) was purchased from Cambridge Isotope Labo-
ratories, Inc. Triethylamine (TEA) was distilled from calcium
hydride under argon. Tetrahydrofuran (THF) was distilled from
benzophenone and sodium metal under argon. AR grade
dichloromethane (DCM), diethyl ether (DEE), 2-propanol,
n-butanol, n-hexane and other solvents were purchased from
Chem-Supply Pty. Ltd. and used as received. The microporous
polyacrylonitrile (PAN) substrate was purchased from SolSep BV
and used without any further treatment.
Scheme 1 The fabrication of a thin film composite blend membrane. (I) The PDMS gutter layer was formed by the cross-linking of amino-terminated PDMS and 1,3,5-
benzenetricarbonyl trichloride (TMC). (II) The thin film composite blend membrane was prepared by spin-coating the mixture of Pebax
2533 and HMA-PEO onto the
PDMS gutter layer.
13770 | J. Mater. Chem. A, 2013, 1, 13769–13778
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Paper
2.2 Measurements
Gel permeation chromatography (GPC) was performed on a
Shimadzu liquid chromatography system tted with a Wyatt
DAWN HELEOS LS detector (l ¼ 658 nm), Shimadzu RID-10
refractometer (l ¼ 633 nm) and Shimadzu SPD-20A UV-vis
detector, using three identical Polymer Laboratories' PLgel
columns (5 mm, MIXED-C) and DMF with 0.05 M LiBr (70  C,
1 mL min1) as the mobile phase. Astra soware (Wyatt Tech-
nology Corp.) was used to process the GPC data and determine
molecular weight characteristics based on the assumption of
100% mass recovery of the polymer. Proton magnetic resonance
spectroscopy (1H NMR) was performed using a Varian Unity
(400 MHz) spectrometer, where the samples were dissolved in
CDCl3. X-ray diffraction (XRD) patterns of the samples were
recorded on a Bruker D8 Advance instrument with Cu Ka
radiation (40 kV, 40 mA) and a nickel lter, and the samples
were exposed at a scanning rate of 2q ¼ 0.020 s1 in the range
of 3–70 . SEM images were acquired using a FEI Quanta 200
ESEM FEG. Samples were pre-coated with gold using a Dynavac
Mini Sputter Coater prior to imaging. X-ray photoelectron
spectroscopy (XPS) analysis was performed on a VG ESCALAB
220i-XL spectrometer under an ultra-high vacuum (6  109
mbar) to reveal the surface composition of the TFC membrane.
A xed photon energy (Al Ka 1486.6 eV) was used. A survey scan
was performed between 0 and 1200 eV with a resolution of
1.0 eV and a pass energy of 100 eV. High resolution scans for C
1s (276 to 296 eV) and O 1s (522 to 542 eV) were also conducted
with a resolution of 0.05 eV and a pass energy of 20 eV.
2.3 Synthesis of multi-block HMA-PEO copolymers
The condensation polymerization of the PEO macromonomer
with terephthaloyl chloride (TCL) occurred under ambient
conditions. A typical example can be described as follows.
PEO400 (2.0 g, 5 mmol; 10 mmol of hydroxyl groups) was dis-
solved in a mixture of 50 mL of anhydrous THF and 4.2 mL of
anhydrous TEA (3.05 g, 30 mmol) under dry nitrogen. TCL
(0.952 g, 4.69 mmol) was dissolved in 10 mL of anhydrous THF
and the solution was added dropwise to PEO solution at 0  C
over 30 min under vigorous stirring. The mixture was then
warmed to room temperature and stirred for a further 24 h. The
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precipitate of triethylamine hydrochloride was removed by 2.5 Gas permeation measurements

ltration. The solution was then concentrated in vacuo (1 mbar)
Single gas permeation measurements of the TFC membranes
and the product was re-dissolved in 50 mL of DCM. The organic
were made using an in-house built constant pressure variable
solution was then washed with H2O (3  50 mL), dried (anhy-
volume (CPVV) apparatus shown in Fig. 1. The TFC blend
drous MgSO4), ltered, concentrated and precipitated into cold
membranes were installed in a stainless cell and were tested for
DEE. Aer removal of DEE, the gel-like polymer was dried in
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single gases (N2 and CO2) under a range of pressures (340 to

vacuo (1 mbar) at 30  C. A colorless product, multi-block HMA-
PEO400 (P1), with an isolated yield of 95% was obtained.
[PEO400]0/[TCL]0 ¼ 16/15; MnTheo ¼ 9.4 kDa; MnGPC ¼ 9.7 kDa,
Mw/Mn ¼ 1.28. For multi-block HMA-PEO1k (P2) [PEO1k]0/[TCL]0
¼ 10/9; MnTheo ¼ 11.8 kDa; Mn GPC ¼ 12.4 kDa, Mw/Mn ¼ 1.36. 1H
NMR (400 MHz, CDCl3, dH ppm): 8.04–8.13 (m, 4H, ArH), 4.41–
4.51 (s, 2H, –CH2O(C]O)–), 3.50–3.74 (m, 4H, –CH2CH2O–).
2.4 Membrane preparation
The cross-linked PDMS gutter layer was coated onto the poly-
acrylonitrile (PAN) microporous substrate as shown in Scheme
S1.† A typical example can be described as follows. In separate
vials, TMC (0.007 g, 0.0267 mmol) was dissolved in 0.35 mL of
hexane (2.0% w/v) and NH2–PDMS–NH2 (0.2 g, 0.04 mmol, 1
equiv.) was dissolved in 10 mL of hexane (2.0% w/v). The two
solutions were then mixed for 30 s and 1 mL of the solution was
then spin-coated (1k rpm, 10 s) onto each PAN substrate
(19.63 cm2) to prepare 10 substrates coated with the cross-
linked PDMS gutter layer. The coated PAN substrates were dried
in vacuo (1 mbar) at 25  C overnight and tested for their gas
transport properties to ensure that there were no leakages
before coating the next layer, the selective layer.
Pebax 2533 was dissolved in a mixture of IPA/n-BuOH (3 : 1
vol.%) at 80  C for 24 h to prepare the polymer solution (2.0 wt%
of Pebax 2533). Aer cooling down the solution to room
temperature, different amounts of the multi-block HMA-PEO (P1
and P2) were added (0 to 66 wt% relative to the amount of Pebax
2533) and stirred at 50  C for 30 min. The IPA/n-BuOH is a binary
solvent which dissolves Pebax 2533 and HMA-PEOs but does not
damage the PDMS gutter layer or the microporous substrate.
1.5 mL of the mixture was then spin coated (1.5k rpm, 20 s) onto
the substrate that had been pre-coated with the PDMS gutter layer.
The TFC blend membranes were then dried in vacuo (1 mbar) at
25  C for 24 h and tested for their gas transport properties.
1000 kPa) and temperatures (35 to 80  C). All data presented in
this work were collected from at least three TFC membranes.
PAN substrates that were pre-coated with the PDMS gutter layer
were also tested with the same gases at 35  C and a pressure of
340 kPa to detect any leakages. The ow rate of the single gases
was recorded manually with a digital ow meter (Agilent
Technologies ADM 2000).
The mass transport in non-porous polymeric membranes
follows the solution-diffusion mechanism that has been well
documented in the literature.26 The ux (J) of a single gas A can
be calculated from eqn (1):
 
Dp
JA ¼ PA (1)
l
where PA is the permeability of gas A in Barrer, Dp is the pres-
sure difference across the membrane in bar and l is the
membrane thickness in mm.
The membrane permeance is dened as the permeability
divided by the membrane thickness and has a unit of GPU. This
permeance can also be expressed in terms of total resistance to
ow (RT) by
 
PA Dp
JA ¼ Dp ¼ (2)
l RT
In turn, the total resistance (RT) to permeation through TFC
membranes can be expressed as the sum of the resistances from
the feed side boundary layer (RF), the permeate side boundary
layer (RP), the membrane selective layer (RSL) and the gutter
layer (RG) coated on the microporous substrate:
RT ¼ RF + RP + RSL + RG (3)
The boundary layer resistances (RF and RP) arise from
concentration gradients that are formed at the surface of the

Fig. 1 Schematic diagram of the apparatus for measurement of gas flow rate.

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Journal of Materials Chemistry A
membrane in mixed gas systems. However, such concentration
polarization is not possible for single gas permeation. Thus the
total resistance to ow is related only to the respective thick-
nesses of the selective and gutter layers and their respective
permeability:28
lSL lG
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RT ¼ RSL þ RG ¼ þ (4)
PSL PG
The resistance to ow through the gutter layer (RG ¼ lG/PG)
can be determined by measuring the ux through this layer
prior to deposition of the selective layer. Eqn (2) and (4) can
then be used to determine the permeance and permeability
through the selective layer, by measuring the ow through the
combined TFC membrane. However, it should be noted that
the estimation of the permeability is highly dependent on the
accuracy in determining the thickness of the selective layer.
The ideal single gas selectivity (aA/B) between two gases A and
B can be expressed by the following equation:
PA
aA=B ¼
PB
3. Results and discussion
In the present study, a commercially available PAN microporous
substrate was employed as a porous support to construct the
thin lm composite (TFC) blend membrane. The solution of
amino-terminated PDMS and TMC was spin-coated onto the
PAN substrate to form a cross-linked gutter layer with high
permeability to CO2 (Scheme 1, step I). This PDMS intermediate
layer could prevent the penetration of diluted polymer solution
into the PAN structure as well as render the entire membrane
surface smoother. Thereaer, the pre-synthesized HMA-PEO
was blended into the Pebax 2533 matrix and the mixture was
then spin-coated onto the PDMS gutter layer to form the TFC
blend membrane (step II). Its ability to selectively separate CO2
from N2 was tested by utilizing an in-house built constant
pressure variable volume (CPVV) apparatus (see Fig. 1).
3.1 Synthesis of the macromolecular precursor
The multi-block HMA-PEO copolymers were prepared via
condensation polymerization of PEOs with TCL, which acts as a
spacer, at room temperature (Scheme 2). PEO crystallinity,
which is typically observed in high molecular weight PEO, is
suppressed by the introduction of the terephthalic spacer. The
low molecular weight PEO block provides exibility which
enables homogeneous dispersion in the Pebax matrix. Two
types of PEOs with different molecular weights (Mn ¼ 400 and
Scheme 2 The synthesis of HMA-PEO copolymers via
polymerization.
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1000 Da, respectively) were employed, allowing the PEO
contents of the multi-block HMA-PEOs to be varied. The resul-
tant HMA-PEOs (P1 and P2) were characterized by GPC for their
molecular weights (MnGPC) assuming 100% mass recovery of
polymers (Table 1). The chemical structure of P1 and P2 was
characterized by 1H NMR analysis. The molar ratio of the PEO
segment to the TCL unit (l) was determined by the integral ratio
of the methylene protons (Hc, dH 4.41–4.51 ppm) adjacent to the
ester group and TCL aromatic protons (Ha, dH 8.04–8.13 ppm)
(Fig. 2 and Table 1). The l values determined by 1H NMR
analysis were slightly higher than the theoretical value from the
feed; the relative difference was reasonably small and within the
error margin. Based on the 1H NMR spectroscopic analysis, P2
has more EO units per polymer chain than P1.
3.2 Preparation of the cross-linked PDMS gutter layer
The PDMS gutter layer was prepared by spin coating the cross-
linkable PDMS solution onto the PAN substrate. The successful
cross-linking of the amino groups was conrmed by XPS
(5)
measurements. The deconvoluted C 1s, O 1s, N 1s and Si 2p
spectra (Fig. S1, ESI†) provided detailed information about
surface functional groups presenting on PDMS, of which all are
in good agreement with the previous literature.29 In order to
estimate the thickness of the PDMS layer, SEM analysis was
carried out on a number of different samples and one image
example is shown in Fig. 3A. The thickness of the PDMS coating
is less than 200 nm. The gas separation performance of the
highly permeable PDMS gutter layer was tested using the
apparatus shown in Fig. 1. The average CO2 permeance reached
up to 2000  100 GPU and the CO2/N2 selectivity was approxi-
mately 9, which are in agreement with the previously published
data30 and demonstrate the successful formation of a PDMS
gutter layer without any leakage.
3.3 Formation and characterization of the selective layer
Pebax 2533 and Pebax 2533/HMA-PEO TFC blend
membranes (P1-25, P1-33, P1-50 and P1-66 in Table 2) were
prepared by spin-coating respective polymer solutions onto the
PAN substrates which were pre-coated with the PDMS gutter
layer. The cross-sectional morphologies of the Pebax 2533 and
P1-50 TFC blend (50 wt% of HMA-PEO) membranes observed by
SEM analysis are illustrated in Fig. 3B and C, respectively. The
thickness of the selective layer was calculated by subtracting the
thickness of the PDMS gutter layer and it was estimated to be
approximately 420 nm in all cases. The chemical changes that
occurred as a result of the coating of the selective layer on the
PDMS gutter layer were further ascertained by X-ray photo-
electron spectroscopy (XPS) analysis. Fig. S2 (ESI†) shows the
high resolution XPS spectra of Pebax 2533 (a, c and e) and P1-
50 (b, d and f). The C 1s and O 1s signals have been altered aer
the coating of the selective layer. For example, new chemical
bonds from the Pebax/HMA-PEO coating were detected. The C
1s spectra signal at 284.8 eV is attributed to the carbon in the
C–C bond, the signal at 286.4 eV is attributed to the carbon
condensation ether bond C–O, the signal at 287.3 eV is attributed to the
carbonyl bond C]O, and the signal at 289.1 eV is attributed to
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Table 1 Summary of characterization results of multi-block HMA-PEOs P1 and P2
Sample Yield (%) MnTheoa (kDa)
P1 95 9.4
P2 92 11.8
a
Determined by feed ratio. b Determined by GPC. c l represents the molar ratio of the PEO segment to the TCL unit obtained by 1H NMR data using
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Ic
the equation l ¼ , where Ia and Ic represent the integral areas of the resonance “a” for aromatic protons of TCL and the resonance “c” for
Ia
methylene group protons (–CH2O(C]O)–) of PEO, respectively.
Fig. 2 1
H NMR spectrum of the multi-block HMA-PEO copolymer P1 in CDCl3.
the carbon in the N–C]O bond. The O 1s spectra signal at
533.0 eV is due to the oxygen in the C–O bond, and the signals at
531.2 eV and 534.0 eV are assigned to the oxygen of C]O and
O–C]O bonds, respectively. In the Pebax selective layer, the
intensity ratio of C–O to C–C signal is 0.73, while the intensity
ratio in the TFC blend membranes, e.g. in P1-50, is 0.85. This
indicates that the selective layer of P1-50 contains a larger
proportion of EO moieties, and thus it is expected to have
higher CO2 permeance.
The crystallinity of the multi-block HMA-PEO copolymers
and the TFC membranes was investigated by X-ray diffraction
(XRD) as shown in Fig. 4. The XRD pattern obtained for the
Pebax 2533 membrane shows three crystalline peaks, which
are attributed to the crystallization of the PA (2q ¼ 22.9 ) and PE
(2q ¼ 17.8 and 26.0 ) segments, respectively. Conversely, the
HMA-PEO copolymer P1 consisted of tens of liquid PEO400
segments and presented as an amorphous phase. Thus its XRD
pattern shows a broad peak around 22.0 . On the other hand, P2
displayed a strong tendency to crystallize due to the crystalli-
zation of its repeat unit, i.e. PEO1k. Its XRD pattern shows a
typical PEO crystalline peak at 2q ¼ 19.2 and 23.6 .31 The P1-50
and P2-50 TFC blend membranes (P1 or P2 50 wt% blend with
Fig. 3 SEM images of the cross-section of the membranes: (A) PDMS gutter layer, (B) Pebax
2533 TFC membrane and (C) P1-50 TFC blend membrane.
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MnGPCb (kDa) Mw/Mnb lc (mPEO/mTCL)
9.7 1.28 1.07
12.4 1.36 1.12
Pebax 2533) show similar XRD patterns to Pebax 2533 and
exhibit no PEO crystalline peaks around 19.2 and 23.6 , indi-
cating a high degree of blending and strong interaction (e.g.
hydrogen bonding and entanglement) between the PEO and
Pebax chain. The XRD investigation provided strong evidence
for the successful suppression of PEO crystallinity by the
condensation polymerization of PEO400. This also indicates that
the crystalline phase of PEO in P2 was eliminated in the blend
system.
It is known that one drawback of using pure PEO in separation
membranes is its strong tendency to crystallize. Previous litera-
ture14 has reported a number of techniques to reduce the crys-
tallinity of PEO, such as utilizing low molecular weight liquid
PEO or designing phase separated block copolymers. In the
present work, we have successfully developed a simple approach
to suppress the crystallization of PEO by condensation polymer-
ization of low molecular weight liquid PEO and TCL.
3.4 Gas transport properties
All the gas transport properties of the TFC blend membranes as
a function of the HMA-PEO mass fraction (0–66 wt%) have been
measured at a temperature of 35  C and a feed pressure of
340 kPa. Fig. 5 shows the CO2 gas permeance and CO2/N2
selectivity for the TFC blend membranes up to 66 wt% HMA-
PEO content relative to Pebax 2533.
As shown in Table 2, the CO2 permeance of these TFC blend
membranes strongly increases with the increase in the HMA-
PEO mass fraction. We hypothesize that the signicant increase
of gas permeance can be attributed to three separate effects.
Firstly, the increase of the HMA-PEO mass fraction results in a
higher overall concentration of EO moieties in the selective
layer. This in turn increases the CO2 solubility for permeation
due to the plasticizing effect of the additive.21 Secondly, the
terephthalic group, which acts as a spacer in the HMA-PEO
polymer, results in a reduction of the PEO crystallinity. Thirdly,
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Table 2 Gas separation performance of Pebax
2533/HMA-PEO TFC blend membranes and their selective layers tested at 35  C and 340 kPa

TFC blend membranesa Selectivity layerb

PEO content CO2 permeance CO2 permeability

Sample (%) CO2 permeance (GPU) CO2/N2 selectivity (GPU) (Barrer) CO2/N2 selectivity lc (nm)
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Pebax 2533 0 305 23 373 157 26 400

P1-25 25 443 24 602 253 28 430
P1-33 33 574 23 914 384 31 440
P1-50 50 899 24 1850 778 40 420
P1-66 66 1130 14 — — — —
P2-25 25 479 23 685 288 29 420
P2-33 33 675 23 1080 452 31 420
P2-50 50 1070 22 2290 960 38 410
P2-66 66 1190 14 — — — —
a
The gas separation permeance of the TFC blend membranes. b The CO2 permeance, permeability and CO2/N2 selectivity of the selectivity layers. c l
is the thickness of the selective layer determined by SEM measurements.

Fig. 4 X-ray diffraction diagrams of Pebax
2533, P1, P1-50, P2 and P2-50.

the HMA-PEO polymer could be readily dispersed in the PA

phase improving the CO2-philic nature of this phase and
increasing the inter-chain distance, which greatly enhanced the
CO2 permeance. The TFC blend membranes containing
between 0 and 50 wt% HMA-PEO copolymers presented a 3 fold
increase in CO2 permeance while maintaining a constant CO2/
N2 selectivity of ca. 23. However, the TFC blend membranes
prepared with 66 wt% HMA-PEOs showed lower CO2/N2 selec-
tivity of ca. 14 with higher CO2 permeance. We believe that this
loss in selectivity resulted from the lack of mechanical stability
of the selective layer for gas permeation experiments.
These results also indicate that there is an optimal content of
the HMA-PEO mass fraction (50 wt%) to fabricate TFC
membranes (P1-50 and P2-50) with desirable CO2 separation
performance. In addition, the P2 series of TFC blend
membranes presented higher CO2 permeance than their P1
counterparts of 50 wt% HMA-PEO blends. The CO2 permeance
increases from 305 to 1070 GPU, ca. 3.5-fold increase, without
loss of selectivity. This is mainly attributed to the higher EO
concentration (see Table 1) in the P2 series, which further
enhances the CO2 solubility of the membrane. The incorpora-
tion of EO units as HMA-PEOs into the Pebax 2533 matrix
clearly resulted in an improvement of gas transport properties.
Fig. 5 CO2 permeance and CO2/N2 selectivity of the TFC blend membranes as a
function of HMA-PEO copolymer (P1 and P2) content tested at 35  C and 340 kPa.
This result is attributed to both structural (increase of EO
concentration) and morphological (decrease of crystallinity)
changes in the selective layer matrix.
3.5 Thermal properties
The effect of gas temperature on membrane performance was
studied in the temperature range of 35–80  C and at a feed
pressure of 340 kPa. The CO2 permeance for Pebax and P1-50
TFC blend membranes versus the experimental temperature is
presented in Fig. 6 and Table 3. Higher temperatures can
enhance the gas permeance due to the increase in polymer
chain mobility and hence the increase in gas diffusivity.32 The
CO2 permeance was increased by 330 GPU in the pure Pebax
TFC membrane and 420 GPU in the P1-50 TFC blend membrane

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Fig. 6 CO2 and N2 permeance and CO2/N2 selectivity of the Pebax
2533 and
P1-50 TFC blend membranes as a function of temperature tested at 340 kPa.
when the operating temperature was increased from 35 to 80  C.
This behavior is typical of non-porous polymeric membranes as
higher gas ux can be recorded with higher temperature.33
Although the CO2 permeance was enhanced with increasing
temperature, the CO2/N2 selectivity of both the Pebax and
P1-50 TFC blend membranes decreased dramatically at high
temperatures. These effects are typical of polymeric
membranes: the reduction in CO2/N2 selectivity is due to the
signicant decrease of both diffusivity and solubility
selectivity.24
3.6 Pressure dependence
As described in the experimental section, single gas (CO2 and
N2) measurements were also carried out across a range of feed
pressures at 35  C. Fig. 7 and Table 4 present the CO2 per-
meance and CO2/N2 selectivity as a function of the feed gas
pressure. The CO2 permeance was increased by ca. 120 GPU in
Pebax and by 200 GPU in the P1-50 TFC blend membrane
when the feed pressure was increased from 340 to 1000 kPa. The
CO2/N2 selectivity of Pebax and P1-50 slightly decreased with
Table 3 Gas separation performance of Pebax
2533 and P1-50 TFC blend membranes tested at 340 kPa
Pebax 2533
Temperature ( C) CO2 (GPU) CO2/N2 selectivity
35 329 25
50 430 18
65 563 14
80 662 11
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Journal of Materials Chemistry A
increasing feed gas pressure. The increasing permeance and
decreasing selectivity are due to CO2-induced plasticization.34
That is, CO2 molecules cause the polymer matrix to swell,
leading to increased FFV and hence increased diffusivity of
gases. However, the change in diffusivity is greater for the larger
gas molecule (N2) resulting in a reduction in the selectivity.
Although plasticization occurred at high feed pressures, the
CO2/N2 selectivity of the TFC blend membrane still maintained
a value of approximately 21 at 1000 kPa. As shown in Fig. 7
(bottom), the change in selectivity of the P1-50 TFC blend
membrane is similar to that of Pebax 2533, which indicates
that the plasticization effect is mainly attributed to the plasti-
cization of the Pebax copolymer and the multi-block HMA-PEO
additive did not induce any further plasticization of the selec-
tive layer.
3.7 Gas permeance and permselectivity of the selective layer
The permeance and selectivity through the selective layer can be
determined by deducting the transport resistances of the gutter
layer. In this study, each of the PAN substrates pre-coated with
the cross-linked PDMS gutter layer was tested for its gas trans-
port properties. The average CO2/N2 selectivity was 9. The ow
resistance through this gutter layer (RG) was determined by
dividing the pressure difference applied across the membrane
by the average ux of CO2 and N2 (eqn (4)). The ow resistance
through the selective layer could then be determined by sub-
tracting this resistance from the total resistance calculated
using the same approach with the TFC blend membrane. The
thickness of the selective layers was estimated by SEM analysis
and the values were in the range of 400–440 nm (Table 2). The
CO2 permeance and permeability of the selective layer were then
calculated and are shown in Fig. 8.
Fig. 8 shows the CO2 permeability, permeance and CO2/N2
selectivity of the selective layer in the fabricated TFC blend
membranes. Both the CO2 permeability and permeance are
enhanced up to six-fold by increasing the HMA-PEO mass
fraction relative to Pebax 2533 (Fig. 8A and B). For example, the
CO2 permeability of the selective layer is increased from 156 to
788 Barrer for the P1 series and to 960 Barrer for the P2 series.
The permeability value of the selective layer, P1-50SL (or P2-
50SL), is much higher than that reported for either cross-linked
PEO (P ¼ 150–270 Barrer)35 or Pebax 2533 (P ¼ 160–180
Barrer).36 This phenomenon can be assigned to the increase in
the proportion of EO moieties, the increase of interaction
between HMA-PEO and Pebax chains, and the decrease of
crystallinity in the selective layer matrix. In addition, the CO2/N2
P1-50
CO2 (GPU) CO2/N2 selectivity
898 25
986 18
1170 13
1320 11
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Journal of Materials Chemistry A
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Fig. 7 CO2 and N2 permeance and CO2/N2 selectivity of the Pebax
2533 and
P1-50 TFC blend membranes as a function of feed gas pressure.
selectivity increased from 25 to 40 (Fig. 8C) with the blending of
the HMA-PEO copolymer up to 50 wt% relative to Pebax 2533
due to the increase of CO2 solubility selectivity in the selective
layer. These unprecedented results, the concurrent increase in
CO2 permeability and CO2/N2 selectivity, present a new direc-
tion for the fabrication of polymeric membranes that surpass
the upper performance limit.
The CO2 permeability of some polymeric membranes
reported in the literature is indicated in Fig. 9.37–39 Fig. 9 also
shows the relationship between CO2 permeability and CO2/N2
selectivity of the selective layer studied in this work when
compared to the data of Robeson's 2008 plots.40 Both the
selective layers P1-50SL and P2-50SL demonstrate exceptional gas
separation performance, surpassing the most recent Robeson
upper bounds of conventional and state-of-the-art polymeric
membranes for CO2/N2 separation. The P1-50SL and P2-50SL also
present higher CO2/N2 selectivity in comparison with the ther-
mally rearranged (TR) polymeric membranes38,41 (hexagon) and
membranes derived from tetrazole modied polymers of
intrinsic microporosity (TZPIMs)37 (circle). In the TFC blend
membranes, the addition of the HMA-PEO copolymer improved
the CO2 solubility and hence increased the solubility selectivity
Table 4 Gas separation performance of Pebax
2533 and P1-50 TFC blend membranes tested at 35  C
Pebax 2533
Pressure (kPa) CO2 (GPU) CO2/N2 selectivity
340 329 25
500 364 22
700 404 22
1000 458 21
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Fig. 8 CO2 permeability (A), permeance (B), and CO2/N2 selectivity (C) of the
selectivity layer as a function of HMA-PEO copolymer (P1 and P2) content tested
at 35  C and 340 kPa.
of the selective layer. However, the Pebax/HMA-PEO selective
layer has less FFV when compared to the TR and TZPIM
membranes, which results in lower CO2 diffusivity and hence
lower CO2 permeability. Nevertheless, the high CO2 perme-
ability (778–960 Barrer) and the reasonable CO2/N2 selectivity
(40–38) for P1-50 and P2-50, respectively, make these polymeric
blends remarkable materials for CO2 separation membranes.
Fig. 10 shows a trade-off plot of CO2/N2 selectivity versus CO2
permeance.8,12 The target area for post combustion capture
proposed by Merkel et al.8 is also included in the plot for
comparison. Membranes require high CO2 permeance ($1000
GPU) and modest selectivity ($20) to fall in this target perfor-
mance area. Membranes with lower CO2 permeances will
require a large membrane area. In addition, membranes with a
selectivity of less than 20 are unlikely to be selective enough,
regardless of their permeance. On the other hand, membranes
P1-50
CO2 (GPU) CO2/N2 selectivity
898 25
961 22
1030 21
1080 21
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Fig. 9 Relationship between CO2 permeability and CO2/N2 selectivity of the
selective layer tested in this study.
with a selectivity of much more than 100 are likely to be too
selective and require a large membrane area because of the
pressure-ratio-issues.
As shown in Fig. 10, the P1-50SL and P2-50SL selectivity layers
have modest selectivity but higher CO2 permeance than the
Polaris membrane (patent protected, no details released),
which in turn is 10–50 times more permeable than conventional
cellulose acetate membranes used for CO2 removal from natural
gas. In comparison with such conventional cellulose acetate
membranes, the Pebax 2533 TFC membrane and its selective
layer (Pebax 2533SL) presented a higher CO2 permeance with
slightly lower CO2/N2 selectivity. The P1-50 and P2-50 TFC blend
membranes showed higher CO2 permeance again (ca. 1000
GPU) with a CO2/N2 selectivity of $20. Their gas separation
Fig. 10 CO2/N2 selectivity versus CO2 permeance plot comparing the perfor-
mance of Pebax
2533, P1-50 and P2-50 TFC blend membranes and their
selective layers Pebax
2533SL, P1-50SL and P2-50SL with commercial natural gas
membranes, the Polaris membrane and developmental membranes reported in
the literature. The target area is that proposed by Merkel et al.8 for post
combustion capture of carbon dioxide. Open circles (B) are data points for Kai
et al.42 and Duan et al.;43 the filled triangle (=) represents data from Bao and
Trachtenberg;44 the filled diamond (A) from Deng et al.;45 the open square (,)
from Cai et al.;46 the open diamond (>) from Hanioka et al.;47 the filled star (+)
from Zhao et al.;48 and the inverted triangles (;) from Hendriks et al.49
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Journal of Materials Chemistry A
performance was close to the target performance area.
Furthermore, the selective layers P1-50SL and P2-50SL displayed
much higher CO2 permeance (ca. 2000 GPU) with a modest
selectivity (ca. 40). This makes the Pebax 2533/HMA-PEO
copolymer mixture in this work an attractive material with
optimum membrane properties for efficient CO2 separation.
It should be pointed out that although the total gas separa-
tion performance of these TFC blend membranes only falls at
the edge of the target area, better separation performance could
be obtained by reducing the thickness of the PDMS gutter layer
or the selective layer. This is an area of our further research.
4. Conclusion
In summary we report a facile approach to prepare Pebax 2533/
HMA-PEO TFC blend membranes for CO2/N2 separation via
spin-coating the mixture onto a PAN microporous substrate that
had been pre-coated with a cross-linked PDMS gutter layer. By
synthesizing a multi-block HMA-PEO copolymer with a tereph-
thalic spacer and using it as an additive, the CO2 permeance was
signicantly increased while maintaining the CO2/N2 selectivity
in the Pebax 2533 based TFC blend membranes. Their ability
to separate CO2 from N2 was studied under variable conditions:
at temperatures of 35–80  C and pressures of 340–1000 kPa. The
highest CO2 permeance with reasonable CO2/N2 selectivity was
found in Pebax 2533/HMA-PEO TFC blend membranes with a
50 wt% HMA-PEO mass fraction. The increased CO2 permeance
was mainly attributed to the increase in the CO2-philic charac-
teristic as a result of the introduction of more EO moieties
and the increase in FFV as a result of an increase in the Pebax
inter-chain distance. In addition, the CO2 permeability of the
selective layer was increased ve-fold and the CO2/N2 selectivity
was increased to 40. This performance of P1-50SL and P2-50SL
successfully surpassed the most recent upper bounds.
Furthermore, P1-50SL and P2-50SL fell within the CO2 separation
performance targets (permeance $1000 GPU and CO2/N2
selectivity $20) with a CO2 permeance of 1800–2200 GPU and a
modest CO2/N2 selectivity, which identies them as promising
materials for efficient CO2 separation.
Acknowledgements
The authors acknowledge the funding provided by the Austra-
lian Government through the CRC program to support this
research. The authors also acknowledge the Australian
Research Council under the Future Fellowship (FT110100411,
G.G.Q.). Q. Fu is the recipient of an Australian Research Council
Super Science Fellowship (FS110200025) and the Australia-
China Emerging Future Leaders in Low Emissions Coal Tech-
nology Fellowship. Q. Fu also wishes to acknowledge the
University of Melbourne's 2013 Early Career Researcher Grant
(Q. Fu).
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