Materials Science and Engineering B 167 (2010) 43–50

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Materials Science and Engineering B

journal homepage: www.elsevier.com/locate/mseb

A novel anion exchange membrane from polystyrene (ethylene butylene)

polystyrene: Synthesis and characterization
Rajangam Vinodh, Arjunan Ilakkiya, Swaminathan Elamathi, Dharmalingam Sangeetha ∗
Department of Chemistry, Anna University Chennai, Sardar Patel Road, Chennai 600025, Tamil Nadu, India

a r t i c l e i n f o a b s t r a c t

Article history: We look forward for an eco-friendly hydrocarbon polymer with higher molecular weight for the prepa-
Received 12 August 2009 ration of an anion exchange membrane. Polystyrene ethylene butylene polystyrene (PSEBS) was chosen
Received in revised form 12 January 2010 as the polymer matrix. The anion exchange membrane was prepared from PSEBS tri-block co-polymer
Accepted 13 January 2010
and then the properties were characterized for alkaline fuel cell application. The preparation of anion
exchange polymer involved two steps namely chloromethylation and quaternization. The anion exchange
Keywords:
membrane with high conductivity has been prepared by introducing quaternary ammonium groups in
Polystyrene ethylene butylene polystyrene
to the polymer. Finally, the membrane was prepared using solution casting method. The solution casting
Dynamic mechanical analysis
Anion exchange membrane
method yields highly hydrophilic membranes with uniform structure that were suitable for electrochem-
Water uptake ical applications. The efficiency of the entrapment was monitored by swelling ratio, chemical stability
Ionic conductivity and ion exchange measurement. The characteristic structural properties of the membrane were inves-
tigated by FT-IR spectroscopy and 1 H NMR spectroscopy. The thermal stability of the membrane was
characterized by TGA, DSC and DMA (dynamic mechanical analysis). The prepared uniform electrolyte
membrane in this study has high thermal and chemical stability. The surface morphology and elemen-
tal composition of the quaternized PSEBS was determined by SEM-EDXA techniques, respectively. The
measured hydroxyl ion conductivity of the synthesized alkaline PSEBS polymer electrolyte membrane
showed ionic conductivity in the range of 10−3 S/cm in deionized water at room temperature. It was
found that the substitution provided a flexible, chemically and thermally stable membrane. Hence, the
membrane will have potential application in the alkaline fuel cell.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction tivity. Unfortunately, they are highly permeable to methanol [2].

Over the past two decades, a tremendous effort in research and
development has been made to improve and commercialize new
systems for generating electricity. To provide an alternative energy
carrier, an appropriate conversion technology is needed to form
high quality power with the highest efficiency and low emission of
pollutants. Fuel cells are good candidates to meet these require-
ments. Fuel cells are electrochemical energy conversion devices
that convert chemical energy directly into electrical energy. The
use of polymer electrolyte represents an interesting path to pursue
studies on electrochemical devices [1]. At present, current research
is focused on developing low cost durable membranes and catalysts
that tolerate a wide range of operating conditions.
The proton exchange membrane commonly used in the pro-
ton exchange membrane fuel cells and direct methanol fuel cells
is the sulphonated polymer, Nafion. It shows excellent chemical,
mechanical and thermal stability along with high ionic conduc-
∗ Corresponding author. Tel.: +91 44 2235 8656.
E-mail address: sangeetha@annauniv.edu (D. Sangeetha).
Recently, a new concept fuel cell using anion exchange mem-
brane and selective electro catalysis has been proposed [3–5].
Alkaline fuel cells (AFCs) are a promising alternative to polymer
electrolyte membrane fuel cells (PEMFCs). Alkaline fuel cells have
several advantages over proton exchange membrane fuel cells on
both cathode kinetics and ohmic polarization [6], such as (i) both
methanol oxidation and oxygen reduction are more facile in highly
alkaline media; electro osmotic drag by OH− is from cathode to
anode, which can reduce methanol cross over from anode to cath-
ode and simplify water management and (ii) non-precious metal
catalysts can be used, which is an advantage over other fuel cells.
These membranes are less expensive and show better mechani-
cal and chemical properties when compared with cation exchange
membranes.
The solid polymer electrolyte membranes are key components
in the development of an electrochemical system. The ion exchange
membrane has been applied to various industrial fields [7]. Some
polymers that exhibit hydrophilic characteristics have received
much attention for electrolyte membrane in recent years [8].
Although commercially available membranes possess excellent
performance and are widely marketed in the whole world, there

0921-5107/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.mseb.2010.01.025
44 R. Vinodh et al. / Materials Science and Engineering B 167 (2010) 43–50
is a demand for membranes that are less expensive and easier
to prepare [9]. Most of the studies to improve the performance
of the ion exchange membrane are about cation exchange mem-
brane because anion exchange membranes (AEMs) are frequently
less stable (the basic groups are inherently less stable than acid
groups) [10]. The purpose of this work is to prepare a novel anionic
exchange membrane by a suitable method and to characterize it.
AEMs can be prepared by several routes: (a) polymer blended
with alkali, (b) pyridinium base type polymer, (c) radiation-grafting
and quaternization of polymer and (d) chloromethylation and quat-
ernization of polymer. Among these, preparation of anion exchange
membrane by chloromethylation and quaternization route is more
advantageous and important because the membrane prepared
by this method has good physical stability and relatively high
chemical stability. The commonly used chloromethylating agent’s
chloromethyl methyl ether (CMME) and bis-chloromethyl ether
(BCME) provides excellent conversions and high yields. But they are
now considered to be carcinogens and their use has been restricted
since the 1970s [11–13].
To avoid the use of such hazardous materials, in our work we
used para-formaldehyde and concentrated hydrochloric acid as
chloromethylating agent as reported by other investigators [14,15].
Further, the prepared AEM based on tri-block co-polymer was ana-
lyzed for application in alkaline fuel cells.
2. Experimental
2.1. Materials
The monodisperse tri-block co-polymer PSEBS having a
number–average molecular weight (Mw ) of 89,000, a molecular
weight distribution (weight-average molecular weight/number-
average molecular weight (Mw /Mn )) of less than 1.06, and 28.6 wt.%
styrene units and composed of two polystyrene (PS) end blocks and
a poly(ethylene-co-butylene) central block, was used as the start-
ing material. Other chemicals like chloroform, methanol, triethyl
amine (TEA), para-formaldehyde, conc. HCl and zinc chloride were
purchased from Sisco Research Laboratory (SRL) Pvt. Ltd. All were of
analytical grade and were used as received. Double distilled water
was used throughout.
2.2. Chloromethylation and quaternization
Chloromethylation reaction of aromatic polymers is an elec-
trophilic substitution at aromatic rings that needs a chloromethy-
lating agent and a Lewis acid catalyst. Chloromethylated PSEBS was
prepared from PSEBS using concentrated hydrochloric acid and
para-formaldehyde as chloromethylating agent and zinc chloride
as catalyst. In order to obtain soluble chloromethylated polymer,
the aromatic tri-block PSEBS (5 g) was dissolved in chloroform;
thereafter 180 mmol of para-formaldehyde and 540 mmol of conc.
HCl mixture was added drop-wise in to the solution with contin-
uous stirring and then 25.3 mmol of zinc chloride was added in
a round bottom flask and the reaction was allowed for 48 h, with
continuous stirring. The reaction temperature was maintained at
60 ◦ C throughout the reaction time. After 48 h, the reaction was
terminated and chloromethylated PSEBS (CMPSEBS) product was
obtained by simply adding the reaction contents into methanol and
washed with methanol to remove the excess acid and formalde-
hyde from the product, after which the product was dried in
vacuum dessicator for a day.
The chloromethylated polymer was dissolved in tetrahydrofu-
ran (THF) and then 25 ml of quaternizing agent, triethyl amine were
added to this solution with continuous stirring. The quaternizing
reaction was carried out in the nitrogen atmosphere at 80 ◦ C for
12 h. The quaternized PSEBS (QAPSEBS) was recovered after remov-
ing all the solvent by evaporation. The product was washed with
water for several times until the pH became neutral. The obtained
ionomer was then dried at room temperature. The schematic repre-
sentation of the preparation of anion exchange membrane is shown
in Fig. 1
2.3. Preparation of anion exchange membrane
Anion exchange membrane was prepared by the solvent casting
method. The purified QAPSEBS was dissolved in THF. The obtained
viscous solution was cast on a clean glass plate and dried at room
temperature. Then the films formed were alkalized by soaking the
QAPSEBS membrane in 1 M potassium hydroxide solution at room
temperature for 24 h. The alkalized PSEBS (ALPSEBS) membrane
was then washed with double distilled water several times prior to
testing.
2.4. Boiling water test and durability test
The boiling water test was carried out by heating the water to its
boiling point, whereas in the durability test the Fenton’s solution
was heated to the temperature of 80 ◦ C and not boiled.
The prepared quaternized polymer membranes were subjected
to exposure in boiling water. The membrane withstood the boiling
water condition, which is in turn a promising result to operate in
the fuel cell environment at higher temperatures.
Ageing test was performed to analyze the durability of the mem-
brane in the fuel cell condition. About 4 ppm of ammonium iron(II)
sulphate hexahydrate in 15 ml of H2 O2 (3%) (Fentons reagent) was
dissolved in 500 ml distilled water containing the quaternized poly-
mer membrane at 80 ◦ C for about 8 h. Durability of the polymer
membrane, which undergoes degradation normally when fuel cell
is operated, can be found out. This test helps in accelerating the
degradation process, there by indicating the mechanical and chem-
ical stability of the membrane over a long period of time in the fuel
cell operating conditions.
2.5. Solvent absorption
A water content study of the membranes was carried out by
measuring the change in weight of the membrane before and after
hydration. It is the process of absorption of large quantities of
solvent by macromolecules, which results in the formation of a
swelled membrane with a considerable increase in volume. The
OH− form of the membrane was immersed in deionized water
at room temperature and equilibrated for more than 24 h. The
wet weight of the membrane was determined after removing the
excess surface water. The percentage water content was calculated
using the following relation. The amount of swelling depends on
the chemical nature of the polymers, the molecular weight and
swelling agent used and on the temperature.
It is calculated by using the formula given below:
Water sorption (%)
Weight of the wet polymer − Weight of the dry polymer
= × 100%
Weight of the dry polymer
2.6. Ion exchange capacity (IEC)
IEC is a measure of the ability of an insoluble material to undergo
displacement of ions previously attached and loosely incorporated
into its structure by oppositely charged ions present in the sur-
rounding solution. Ion exchange capacity was determined by a
 R. Vinodh et al. / Materials Science and Engineering B 167 (2010) 43–50
Fig. 1. Schematic representation for synthesis: chloromethylation, quaternization and alkalization of PSEBS.
back-titration method [16]. The dried and weighed polymer mem-
brane (in hydroxide form) was immersed in 100 ml of 0.01 M HCl
standard for one day and was allowed to get converted to Cl− form.
The anion exchange capacity was determined from the decrease in
acidity, which was obtained by back titration after neutralization
of the membrane. The ion exchange capacity of the anion exchange
membrane was calculated by using the formula given below:
Titer value (ml) × Normality of titrant (NaOH)
IEC = mequiv./g
Weight of the dry polymer membrane (g)
2.7. Structural confirmation
The chemical structure of the membrane was analyzed using
FT-IR. The FT-IR spectra of PSEBS, CMPSEBS and QAPSEBS were
recorded in transmission mode using PerkinElmer spectrome-
ter by placing the membranes in KBr windows. Confirmation of
chloromethylation and quaternization was also done by 1 H NMR
spectroscopy. Proton NMR (1 H NMR) spectra were obtained with
Bruker NMR spectrometer using deuterated chloroform as the sol-
vent.
2.8. Thermo gravimetric analysis (TGA)
This is the technique in which the change in weight of a sub-
stance with temperature over a period of time is followed. Thermal
stability and decomposition temperature of the polymer can be
45
assessed easily using this technique. The TGA thermal analysis was
carried out using TGA model Q50 V20.6 build 31 system. The mea-
surements were conducted by heating from room temperature to
800 ◦ C at a heating rate of 10 ◦ C/min under nitrogen atmosphere.
2.9. Differential scanning calorimetry (DSC)
This is a technique in which the heat capacity of the polymer is
measured as a function of temperature. Tg of polymer can be deter-
mined by this method. DSC spectra were obtained on DSC model
NETZSCH-Geratebau Gmbh thermal analysis. Measurements were
performed in nitrogen atmosphere at a heating rate of 20 ◦ C/min.
2.10. Dynamic mechanical analysis (DMA)
Dynamic mechanical analysis (DMA) was performed with a
NETZSCH DMA 242 mechanical spectrometer under nitrogen atmo-
sphere. The flow intention mode was set at a frequency of 1.0 Hz
with the sample dimension of 25 mm × 3 mm at temperature rang-
ing from room temperature to 300 ◦ C at a heating rate of 5 ◦ C/min.
The static force was set to be 4 N.
2.11. Morphology study
A scanning electron microscopy was used to investigate the sur-
face morphology of membranes. SEM micrographs were obtained
46 R. Vinodh et al. / Materials Science and Engineering B 167 (2010) 43–50
with the help of HITACHI S-3400 with associated energy dispersive
X-ray analyzer. QAPSEBS was dried and then coated with gold to
achieve SEM images. EDXA analysis was based on silica drift cham-
ber technology with no external cooling. An X-ray beam of 20 kV
and a scanning rate of 30 frames per second was used. Quantitative
analysis software was used to sort out the displayed pixels as X-ray
and to calculate elemental composition.
2.12. Conductivity measurements
The hydroxyl conductivity measurement is similar to the pro-
ton conductivity measurement using the normal four-point probe
technique [17]. Hydroxyl ion conductivity of the membrane was
determined using AC impedance spectroscopy. Before testing, the
OH− form of the membrane was hydrated in deionized water for
24 h. The testing device with the membrane was placed in deionized
water to keep the relative humidity at 100% during the measure-
ments. From the difference between the resistance of the blank
cell and the one with membrane separating the working and the
counter electrode compartments, the resistance of the membrane
was calculated and converted to conductivity values using the for-
mula:
L (5.74%), followed by the quaternized PSEBS (4.04%), chloromethy-
Conductivity (S/cm) =
R×A
where R = sample resistance (), L = wet sample thickness (cm) and
A = sample area (cm2 ).
3. Results and discussion
As mentioned in Section 2, the novel anion exchange mem-
brane was prepared from PSEBS. The three steps in the preparation
of anion exchange membrane include (i) chloromethylation, (ii)
quaternization and (iii) alkalization. Polystyrene ethylene buty-
lene polystyrene was chloromethylated by nHCHO, Conc. HCl
(chloromethylating agent) and ZnCl2 (catalyst) then quaternized
by triethyl amine. The degree of substitution depends on many
parameters such as reaction time, temperature, concentration of
chloromethylating agent and polymer concentration. After opti-
mization of these parameters, the PSEBS polymer was successfully
chloromethylated to an appropriate level. The possible reaction
steps are shown in Fig. 1.
Hydrolytic stability of the membrane was investigated by intro-
ducing the membrane in to boiling water. It was found that the
QAPSEBS withstood the boiling water condition without any phys-
ical deformation, which means that the structure of polymer makes
the QAPSEBS membrane to have good hydrolytic stability. Hence it
is inferred that the membrane can be safely used in the fuel cell at
higher temperatures (80–100 ◦ C).
Ageing test involves acceleration of the degradation process,
thereby indicating the mechanical and chemical stability. The
QPSEBS ionic membrane was introduced in to 3% hydrogen perox-
ide with 4 ppm ammonium iron II sulphate hexahydrate (Fenton’s
reagent) dissolved in 500 ml distilled water at 80 ◦ C. The ionic mem-
brane does not have any physical deformation and the membrane
was stable for more than 8 h.
The properties measured were IEC, water absorption and ionic
conductivity. The results obtained after boiling and durability of the
membrane were not significantly changed, which means that the
prepared QAPSEBS membrane has good mechanical and chemical
stability.
3.1. Water absorption and IEC
Water uptake of PSEBS, CMPSEBS, QAPSEBS and ALPSEBS mem-
branes were shown in Fig. 2. Water absorption capacity depends on
Fig. 2. Water uptake of PSEBS, CMPSEBS, QAPSEBS and ALPSEBS membranes.
the presence of number of ion exchange groups present in the mem-
brane. The alkalized PSEBS showed the highest water absorption
lated PSEBS (2.25%) and the base PSEBS (0.49%). This percentage
variation may be attributed to the nature of functional group that
each polymer carries. Apparently, ALPSEBS is the most polar poly-
mer, while PSEBS is the least polar. Although, QAPSEBS contained
Cl− , this anion is much less active than the OH− on the alkalized
polymer when interacting with water [18]. This water absorption
indicates that the introduction of quaternary ammonium group
converts the hydrophobic PSEBS in to hydrophilic.
Experimental ion exchange capacity value was calculated for
the QAPSEBS by titration method. IEC can provide information on
the density of ionizable functional group in the membrane. The
IEC displayed a linear relationship with hydroxyl ion conductivity
and water absorption. IEC of the membrane depends on the num-
ber of ionic channels present in the membrane, which are in turn
responsible for the hydroxyl conductivity of the membrane through
hopping mechanism. The ion exchange capacity of the prepared
membrane (APSEBS) was found to be 0.578 mequiv./g.
3.2. FT-IR
PSEBS, CMPSEBS and QAPSEBS samples were characterized
by FT-IR. The FT-IR spectra were determined to confirm the
chloromethylation and quaternization of the polymer and the
resulting spectra was shown in Fig. 3. The following conclusions
were drawn from the obtained spectra.
Fig. 3(a) shows the IR spectrum of PSEBS. Appearance of peak
around 1638 cm−1 was assigned to the aromatic ring C C. Appear-
ance of peak around 1458 and 1366 cm−1 was assigned to the
bending vibration which is due to the presence of aromatic ring
backbone –CH– bending vibration. The peak at 2924.23 cm−1 is due
to the stretching of C–H bond of aromatic hydrocarbon. Appearance
of peak around 699 and 747 cm−1 was assigned to the aromatic
ring out of plane C–H bending vibration. Appearance of these peaks
confirmed the structure of PSEBS.
Due to chloromethylation reaction (Fig. 3b), the IR bands of C C
in aromatic ring from styrene unit are shifted to a lower frequency
in the range of 1601 cm−1 . As well as the IR bands of the aromatic
ring backbone CH bending vibration, are shifted to a lower fre-
quency in the range of 1404 and 1247 cm−1 . This confirms that the
reaction has occurred in the aromatic ring. Appearance of peak at
1247 cm−1 shows that the CH2 Cl group is substituted at the phenyl
ring.
 R. Vinodh et al. / Materials Science and Engineering B 167 (2010) 43–50 47

Fig. 3. FT-IR spectra of PSEBS (a), CMPSEBS (b), and QAPSEBS (c).

Due to quaternization reaction, the IR bands of aromatic ring

C C and aromatic ring backbone –CH– bending vibration are
shifted to a lower frequency around 1600 and 1371 cm−1 . In this
reaction, triethyl amine is used to form the quaternized product. IR
bands for tertiary amine cannot be seen in the spectrum. Appear-
ance of peak around 1371 cm−1 was assigned to C–N stretching
vibration. Due to the quaternization (Fig. 3c), a small intense peak at 1
Fig. 4. H NMR spectra of PSEBS (a) and QAPSEBS (b).
2365.72 cm−1 has appeared, which is the characteristic absorption
peak of quaternary ammonium groups. From all these evidences,
it is clear that chloromethylation and quaternization reactions 3.4. Thermo gravimetric analysis
have been successfully carried out in the PSEBS unit at phenyl
rings. The thermal degradation of CMPSEBS and QAPSEBS was stud-
ied with thermo gravimetric analysis. Fig. 5 shows the thermo
gravimetric curves of PSEBS, CMPSEBS and QAPSEBS. The PSEBS
3.3. Nuclear magnetic resonance polymer shows a major decomposition in TGA curve from 416
to 459 ◦ C which may be due to the polymer degradation. The
Fig. 4 shows the NMR spectra of PSEBS and QAPSEBS. By chloromethylated PSEBS also shows a sharp single step decompo-
characterizing the polymer samples of PSEBS and QAPSEBS with
proton nuclear magnetic resonance spectroscopy, the following
conclusions were drawn. The base polymer PSEBS contains 29% of
polystyrene and 71% of ethylene and butylene. Since the styrene
content is only 29%, it shows a very low intensity in NMR bands.
The solvent peak appears at ı = 7.28 ppm. The alkyl proton bands
namely CH3 proton, CH2 proton and CH proton are appearing at
0.9, 1.3 and 1.5 ppm, respectively. The bands that appear in the
region between 6 and 8.5 ppm are due to the aromatic ring protons.
Appearance of these proton bands clearly confirms the structure of
the PSEBS.
Due to quaternization reaction, some structural changes takes
place in the reactant PSEBS. Appearance of a new triplet peak at
1.3 ı is assigned to the CH3 protons from N–CH2 –CH3 group. The
new peak appears at 4.1 ı is assigned to the CH2 –N protons due
to the presence of the phenyl group. The quartet band formed at
3.0 ı is assigned to the N–CH2 –CH3 group. All these confirm the
structure of QPSEBS. In summary, the changes in NMR spectra sup-
port the chemical modification of PSEBS in to an anion exchange
polymer. Fig. 5. Thermo gravimetric curves of PSEBS, CMPSEBS and QAPSEBS.
48 R. Vinodh et al. / Materials Science and Engineering B 167 (2010) 43–50

sition at 425 ◦ C without leaving any residue. This is due to the main
chain decomposition. The decrease in thermal stability of CMPSEBS
is due to the introduction of polar group in to the polymer chain,
whereas, the QAPSEBS shows a two step degradation. The first
weight loss between 70 and 190 ◦ C is due to the removal of qua-
ternary ammonium groups from the polymer [15] and the second
weight loss observed at temperature higher than 460 ◦ C, is due to
the complete degradation of the polymer chain. The curves demon-
strate that the QAPSEBS has moderate thermal stability and higher
degradation temperature. This suggests that the QAPSEBS based
anion exchange membrane is suitable to work in alkaline fuel cell
conditions.

3.5. Differential scanning calorimetry

The thermal behavior of the PSEBS CMPSEBS and QAPSEBS were

Fig. 7. storage modulus vs. temperature at 1 Hz for (a) PSEBS and (b) QAPSEBS
studied using DSC. The Tg value for PSEBS (Fig. 6a) was found to be
membrane.
78 ◦ C, whereas for CMPSEBS (Fig. 6b) it was 124 ◦ C. The remarkable
increase in the Tg value could be attributed to the electronega-
tive nature of the –CH2 Cl group. On the other hand, for QAPSEBS
3.6. Dynamic mechanical analysis
(Fig. 6c), due to the bulkiness of the quaternized group, a lowering
in the Tg value (86◦ C) was observed. Hence a moderate Tg value
Dynamic mechanical analysis is used to measure the defor-
obtained for QPSEBS is an evidence for the adequate thermal prop-
mation of a material in resonance to vibrational forces. The
erty of QAPSEBS for AFC application. From Fig. 6c it may be inferred
dynamic modulus, the loss modulus and a mechanical damping
that the crystallization temperature of QAPSEBS 100◦ C and the
or internal friction were determined from these measurements.
melting temperature was observed to be 210◦ C.
The mechanical damping (internal friction) gives the amount of
energy dissipated as heat during the deformation. These dynamic
parameters have been used to determine the glass transition
region, relaxation spectra, degree of crystallinity, molecular orien-
tation, cross linking, phase separation, structural or morphological
changes resulting from processing, and chemical composition in
poly blends, graft polymers and co-polymers [19].
Fig. 7 shows the temperature dependence of the storage mod-
ulus E of the PSEBS (Fig. 7a) and QAPSEBS (Fig. 7b) membrane.
The ionomer (QAPSEBS) displays typical behavior of an amorphous
polymer. In the glassy state, the storage modulus E remains roughly
constant. The Tg value of PSEBS and QAPSEBS were found to be
77 and 86 ◦ C, respectively, which are close to each other. In the
temperature vs. storage modulus plot the two curves belonging
to PSEBS and QAPSEBS were found to be close to each other. This
is an indication that the Tg values of the two polymeric materi-
als were close. The storage modulus is an indication of the rigidity
of the material. Upon increasing the temperature from 30 to 200◦
C there is a decrease in the storage modulus. The storage modulus
was found to be around 5 MPa when the temperature reaches 105 C
for PSEBS and about 3 MPa for QAPSEBS at 120◦ C. Around 45 ◦ C,
the modulus drop is associated with the glass-rubber transition

Fig. 6. DSC curves of PSEBS (a), CMPSEBS (b) and QAPSEBS (c). Fig. 8. Tan delta vs. temperature at 1 Hz for (a) PSEBS and (b) QAPSEBS.
 R. Vinodh et al. / Materials Science and Engineering B 167 (2010) 43–50
Fig. 9. SEM micrograph: Surface view (a) and cross-sectional view (b) of membrane in Cl− form.
of the ionomers. This modulus corresponds to energy dissipation
displayed in a relaxation process [1].
The properties of the polymers change with temperature. In par-
ticular, it has been found that the coefficients of thermal expansion
of amorphous polymers undergo abrupt changes in the region of the
glass transition. The temperature at this abrupt change is defined as
glass transition temperature, Tg . From the Fig. 8, it is observed that
QAPSEBS (Fig. 8b) membrane shows an inflection point at 86 ◦ C,
where the internal friction (tan ı) curve goes through a maximum.
This value corresponds to the glass transition region of the QAPSEBS
membrane. The Tg values obtained from DMA is more accurate. The
Tg values for PSEBS (Fig. 8a) and QAPSEBS from DMA were found to
be 82 and 86 ◦ C and were in good agreement with the DSC values.
3.7. Membrane morphology
The surface morphology of the QAPSEBS membrane was stud-
ied by scanning electron microscopy. Fig. 9(a) and (b) shows the
SEM-EDXA photographs of QAPSEBS with two different magnifica-
tion levels such as 20 and 50 ␮m, respectively. Fig. 9(a) shows the
surface morphology of the QAPSEBS. The SEM photograph shows
a uniform surface and Fig. 9(b) shows the cross-sectional image
of QAPSEBS, which also confirms the uniformity of the membrane.
These micrographs show rough fractured surfaces, which provide
Fig. 10. Ionic conductivity of the anionic membrane in OH− form.
49
some information regarding membrane’s mechanical properties
[20]. The cross-sectional view of the QAPSEBS membrane show par-
tially penetrating holes, which become the anion exchange channel
[21].
3.8. Ionic conductivity
On introducing the quaternary ammonium groups in to the
polymer chain, the hydroxyl ion conducting ability was introduced.
Fig. 10 shows the impedance spectrum of the formed ALPSEBS
anion exchange membrane at room temperature and 100% humid-
ity. To examine the conductivity, the quaternized membrane was
first soaked in KOH solution for 24 h to convert in to OH− form
and then it was washed several times with deionized water. After
the free KOH was completely removed, the conductivity of the
membrane was measured. This novel anion exchange membrane
showed conductivity with the value of 0.69 × 10−3 S/cm. Hence,
this novel anion exchange membrane can be potentially used for
alkaline fuel cell applications.
4. Conclusion
The present study deals with the preparation of hydrocarbon-
based QAPSEBS polymer membrane for alkaline fuel cell appli-
cation. A novel QAPSEBS anion exchange membrane has been
successively prepared viz. chloromethylation, quaternization and
alkalization and the membrane was prepared using solution cast-
ing method. The solid polymer electrolyte membrane has show
low ionic conductivity due to low ion exchange capacity value at
room temperature. In this work, PSEBS was chemically modified
and characterized in order to prepare an anion exchange membrane
polymer electrolyte with defined characteristics. By microscopy we
concluded that the membrane has uniform surface and does not
observe any noticeable damage in the membrane. The modified
polymer has been characterized by FT-IR, NMR, thermal analysis
and electrochemical methods. The results show that the mem-
brane is potentially useful for the application in anion exchange
membrane fuel cell due to their ionic conductivity and high ther-
mal stability. Further optimization of the membrane conductivity
will allow the successful application in alkaline fuel cell. The mem-
brane was characterized by conventional properties such as water
uptake, IEC and other fuel cell related performances such as con-
ductivity and stability. The ionomer showed good thermal stability
upto 190 ◦ C. The results show that the membrane can be consid-
ered as a promising alternative anion membranes for alkaline fuel
cells. Further work need to focus on enhancing the stability and
50 R. Vinodh et al. / Materials Science and Engineering B 167 (2010) 43–50
conductivity of this new anion exchange membrane, evaluating its
mechanical strength and fuel cell applications.
Acknowledgement
Financial support from the Department of Science and Technol-
ogy (DST), New Delhi, India (Letter No. SR/S2/CMP-06/2008, dated
21-08-2008) is gratefully acknowledged.
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