EUROPEAN

POLYMER
European Polymer Journal 41 (2005) 2644–2652
JOURNAL
www.elsevier.com/locate/europolj

Conductivity and solvent uptake of proton

exchange membrane based on polystyrene(ethylene–butylene)
polystyrene triblock polymer
D. Sangeetha *

Department of Chemistry, Anna University, Sardar Road, Chennai 600 025, India

Received 11 March 2005; accepted 31 March 2005

Available online 10 August 2005

Abstract

Conducting membranes of polystyrene-block-(ethylene-ran-butylene)-block-polystyrene were obtained by sulphona-

tion of the polymer using chlorosulphonic acid. The membranes were found to have an excellent conductivity in the
order of 10
1 S/cm in their fully hydrated condition at room temperature as measured by impedance spectroscopy. This
value is several orders higher than what is reported in the literature for hydrocarbon based ionomers. Water and meth-
anol absorption of both non-reinforced and reinforced membranes were studied. Maximum uptake of solvents, wet
membrane porosity and uptake of solvent molecules per sulphonic acid group were calculated gravimetrically. Charac-
terization of the membranes was performed by IR, DSC and TGA methods.

2005 Elsevier Ltd. All rights reserved.

Keywords: Sulphonated polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene; Conductivity; Solvent absorption; Poros-

ity; Proton exchange membrane fuel cell

1. Introduction ical strength, dehydration resistance, chemical stability

and fuel permeability along with a reasonably low cost.
Development of proton exchange membrane fuel cell Nafion, a perfluorosulphonic acid ionomer [4–6] by far,
(PEMFC) as power sources for electric vehicles has been has been the standard membrane of extensive study for a
the subject of much attention during the last decades long time due to their high proton conductivity. The
mainly due to the environmental aspects [1–3]. Substan- major disadvantage of Nafion membranes is their high
tial progress however, is still required to reduce the man- cost. Hence, much effort has gone into the development
ufacturing cost and to improve the performance before of proton exchange membranes based on low cost
the commercialization of fuel cell vehicles. Although, materials.
there are a number of protonic membranes, membranes Several block ionomers, which are considerably
in todayÕs most advanced PEMFC do not possess the re- lower in cost, have been studied in literature due to their
quired combination of high ionic conductivity, mechan- unique morphologies arising due to the combination of
both hydrocarbon block and ionomer block in their
structure [7–12]. Polystyrene(ethylene–butylene)polysty-
*
Tel.: +91 44 22203158; fax: +91 44 222006600. rene (PSEBS) is a tri-block polymer. The complexation
E-mail address: [email protected] behaviour of the sulphonated PSEBS ionomer has been

0014-3057/$ - see front matter
2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2005.03.018
 D. Sangeetha / European Polymer Journal 41 (2005) 2644–2652 2645

reported by a number of authors [13–17]. The solution value of 4.65 · 10
5 S/cm (without water) in dry condi-
and solid-state properties of the polymer have also been tion to 1.4 · 10
2 S/cm with 12 mass% water content.
studied widely [18–21]. Mani et al. have reported the Hence, the maximum uptake of water becomes more
small angle X-ray scattering studies on microstructures important in determining the conductivity of the mem-
of sulphonated PSEBS and its ionomers [22]. Other brane. In this report, we have studied the maximum
block ionomers under study for the PEMFC application capacity of the membranes to retain the water molecules
include poly(styrene-block-ethylene-co-propylene) [23] with themselves at different temperatures. Wet mem-
and hydrogenated poly(butadiene–styrene) copolymer brane porosity and water/methanol fluid uptake were
[24,25]. determined at room temperature from the dried and
The sulphonated styrene(ethylene-block-butylene)- solution equilibrated membranes without reinforcement.
styrene polymer prepared by Ehrenberg et al. [26,27] The overall uptake of solution molecules per sulphonic
using SO3 as the sulphonating agent has been claimed acid group was also calculated.
to have the proton conductivity in the range of 10
5 S/cm In this paper, we report the synthesis of sulphonated
in its fully protonated state. The membrane has been PSEBS by sulphonating the styrene blocks of the poly-
reported to absorb 50% of its weight in water. The mer by ClSO3H acid. The membranes obtained from
thermal stability of the ionomer was improved by the ionomer shows an excellent proton conductivity of
impregnating tetraethyl orthosilicate in the polymer the range 10
1 S/cm. The sulphonated ionomer was also
membrane by Jung et al. [28]. The structure of the sulph- reinforced with glass fiber mat to improve the stability of
onated polymer is shown in Fig. 1. Recently, Smitha the membrane in its hydrated state without any reduc-
et al. [29] have reported the sulphonation of polyether tion in conductivity. Water and methanol uptake of
ether ketone (PEEK) using sulphuric acid. According both non-reinforced and reinforced membranes were
to Falus et al. [30], microstructure of the blends of tri analyzed on a comparison basis.
block copolymer, poly(styrene–ethylene butylene–sty-
rene) with homopolymer, polystyrene reveals a sponge-
like morphology. 2. Experimental
Proton conductivity of a proton exchange membrane
highly depends on the water content of the sulphonic 2.1. Synthesis of ionomer
acid ionomer. The ionomer serves more as a matrix
for a proton-conducting medium than as the medium it- Sulphonation of polystyrene-block-poly(ethylene-
self. Ionomers show poor ionic conductivities at low ran-butylene)-block-poystyrene (PSEBS) (Aldrich,
humidity and/or elevated temperatures [31–33]. Conduc- Styrene 29 wt.%, Mw = 89,000) was conducted in chlo-
tivity of Nafion 117 and a structurally similar polymer, roform employing chlorosulphonic acid as the sulpho-
bis(perfluoroalkyl)sulfonylimide ionomer were found to nating agent. A number of experiments were
strongly depend on humidity and temperature [34]. This performed to determine the optimum conditions of sul-
dependence can be understood in terms of ‘‘liquid-like’’ phonation of PSEBS, by varying the solvent, polymer
mechanism [34,35] of proton conductivity whereby pro- concentration, reaction time and the amount of sulpho-
tons are transported as hydrated hydronium ions nating agent. After dissolving PSEBS in chloroform, the
through water filled ionic pores and channels. Conduc- solution was allowed to cool to 0 C in an ice bath. (Ice
tivity and water uptake properties of membranes based bath was maintained throughout the duration of the
on sulphonated polymers including polyetheretherke- reaction.) Then required amount of tri-butyl phosphate
tone, polyethersulfone and polyphenylquinoxaline were (to moderate the reaction) followed by chlorosul-
reported by Kopitzke et al. [36]. The swelling and con- phonic acid (Spectrochem Pvt Ltd., India) was added
ductivity characteristics of sulphonated polyimide mem- drop-wise over a period of time. Continuous stirring
branes were determined to depend on the ionic content was maintained during the reaction. The reaction pro-
and ion distribution along the polymer chain [37]. The ceeded for 2 h and was terminated by adding a lower ali-
conductivity of the inorganic–organic protonic polymer phatic alcohol. The sulphonated PSEBS was recovered
electrolyte developed by Depre et al. [38] rose from a after removing all the solvents by evaporation. The com-
plete removal of residual acid from the product obtained
after sulphonation is important since it can interfere
with the properties of the final product. The removal
of residual acid was checked for neutral pH as follows.
The product was washed 4–5 times with water, followed
by washing for half an hour in boiling water and again
several washings with water until a neutral pH is ob-
tained. The product was then dried at 75 C for several
Fig. 1. Structure of sulphonated polymer. hours.
2646 D. Sangeetha / European Polymer Journal 41 (2005) 2644–2652

2.2. Preparation of membrane sphere. A NETZCH TG 209C thermogravimetric ana-

lyzer was used to analyze the stability of polymers at a
Required amount of sulphonated polymer was heating rate of 20 K/min under nitrogen.
weighed and dissolved in a suitable solvent mixture of
predetermined concentration. After one full day, the 2.5. Protonic conductivity
content resulted in a highly viscous solution. Membrane
is cast from this solution by solvent casting technique. Proton conductivity of the membranes was deter-
The polymer solution is cast onto preferably a glass mined by a complex impedance spectra obtained using
plate of smooth surface. Membranes of varying thick- Voltalab Dynamic-EIS Voltammetry Model PGZ 301.
ness (100–500 lm) could be obtained by varying the Studies were carried out using a 2-compartment electro-
amount of solution used. chemical cell, using platinum foil electrodes and 1 M sul-
During the formation of membrane, several problems phuric acid solution as the electrolyte.
like unevenness, veins, voids, thin regions, cracks and air
bubbles, were encountered, which directly affect the 2.6. Leaching experiment
quality of the membranes. To rectify these problems
during the fabrication of membranes, after casting the Leaching experiment was performed in order to con-
solution, the membranes were subjected to a very slow firm the proton conductivity of the membranes even
evaporation of the solvent over a period of 24 h. For after storing them in water for many days. The water
this, an atmosphere of the solvent above the cast solu- was freshly changed everyday. Conductivity of the mem-
tion was maintained throughout its long drying time. brane was tested at regular intervals of time.
Prior to their use in conductivity experiments, all the
samples of sulphonated PSEBS membranes were pre- 2.7. Solvent uptake measurement
treated by boiling for over half an hour in each step in
3% hydrogen peroxide (to oxidize and remove any or- Solvent absorption studies were carried out gravimet-
ganic contaminants); in water; in 0.3 M sulphuric acid rically. Membranes were dried at 75 C overnight and
(to remove any metallic impurities); and again in water then weighed for their dry weight (Wdry) and then were
(to rinse away the excess acid). immersed in respective solvents for 24 h, to reach the
equilibrium. The saturated membranes were blotted
2.3. Ion exchange capacity and degree of sulphonation carefully to absorb all surface bulk solvent and weighed
for the wet weight (Wwet). The solvent absorption of the
The ion exchange capacity (IEC) indicates the num- membrane was then expressed as the percent ratio of
ber of milli-equivalents of ions in 1 g of the dry polymer. weight increase to that of its weight, i.e.,
The degree of sulphonation (DS) indicates the average
W wet
W dry
number of sulphonic groups present in the sulfonated Solvent absorption ¼  100% ð1Þ
polymer. They were determined by titration method. W dry
The membrane in its acid form was weighed and then
Wet membrane porosity (e) and water/methanol fluid
soaked in an aqueous solution containing a large excess
uptake were also calculated at room temperature [39]
of KCl salt in order to extract all protons from the mem-
using the equation given below.
brane. The electrolyte solution was then neutralized
using a very dilute Na2CO3 solution of known concen- Fluid uptake volume
e¼
tration. The EW (equivalent weight) values were calcu- Total volume
lated from the dry weight of the membrane divided by ðW wet
W dry Þ  qdry
the volume and the normality of the Na2CO3 solution. ¼ ð2Þ
ðW wet
W dry Þ  qdry þ ðW dry  qsol Þ
The IEC values were expressed as meq. of sulphonic
groups per gram of dry polymer. The DS values where, qdry is the dry membrane density (0.910 g/cm3 for
were also reported. It is the number of sulphonated PSEBS assumed for the dry membrane) and qsol is the
units per 100 monomer units and is expressed as solution density. The overall uptake of solution mole-
percentage. cules per sulphonic acid group in the membrane (ktotal)
was calculated using Eq. (3).
2.4. Characterization of polymers ðW wet
W dry Þ EWMembrane
ktotal ¼  ð3Þ
W dry 18vwater þ 34ð1
vwater Þ
FTIR spectra of thin polymer films were obtained on
a Bruker Vector 22 Spectrophotometer for both un-sul- where, vwater is the molar fraction of water in the solu-
phonated and sulphonated polymer samples. DSC mea- tion and EWMembrane is the equivalent weight of the
surement was carried out at a heating rate of 20 K/min membrane. The uptake of water molecules per sulphonic
with a NETZCH DSC 200 PC under nitrogen atmo- acid group (kwater) and uptake of methanol molecules
 D. Sangeetha / European Polymer Journal 41 (2005) 2644–2652 2647

per sulphonic acid group (kmethanol) were then calculated 699 cm
1 and 760 cm
1 on sulphonation indicated the
from ktotal using Eqs. (4) and (5) substitution in the aromatic ring when compared to
the un-sulphonated sample. Fig. 3 shows the DSC
kwater ¼ ktotal .vwater ð4Þ curves of the samples studied. The inflection point of
the slope change of the heat capacity plot was taken as
kmethanol ¼ ktotal  ð1
vwater Þ ð5Þ
the Tg and it was around 71 C for the un-sulphonated
polymer and about 98 C for the sulphonated one.
2.8. Water desorption measurement Hence, sulphonation increases the Tg of the polymer
due to the larger sulphonic acid group present in the sul-
The sample membranes were immersed in water at phonated polymer. The TGA curves of the polymer
room temperature for 24 h to reach the saturation point. samples are shown in Fig. 4. The thermal decomposition
Then, the membranes were weighed for their wet weight, temperature of the membrane is a function of sulphona-
and were allowed to dry at different temperatures for tion. The un-sulphonated sample display thermal stabil-
about 10 h. The samples were weighed at regular inter- ity up to 350 C, but the sulphonated membrane loses
vals of time, until the membrane reaches a constant its stability beyond 250 C. A small transition around
value. This value is also the dry weight of the membrane. 100 C in the sulphonated and sample is attributed to
The water desorption of the membrane was then ex- the presence of moisture. The transition around 250 C
pressed as the percent ratio of weight decrease to its wet may be due to the thermal degradation of sulphonic acid
weight, i.e., groups. The transition around 400 C is attributed to
main chain scission. Thus, sulphonation decreases the
W wet
W dry
Water desorption ¼  100% ð6Þ thermal stability of the polymer due to the degradation
W wet of the sulphonic acid groups at lower temperatures.
However, the sulphonated hydrocarbon polymer mem-
brane has adequate thermal properties for application
3. Results and discussion in fuel cells, since their thermal decomposition is de-
tected only above 230 C.
3.1. Characterization of polymers
3.2. Conductivity studies
Fig. 2 shows the IR spectra of un-sulphonated and
sulphonated PSEBS samples. Appearance of bands at Ion exchange capacity (IEC), which is a measure of
1007 cm
1, 1031 cm
1 and 1126 cm
1 in the sulpho- degree of sulphonation as determined by the titration
nated sample indicated the sulphonation of the phenyl method was found to be greater than 1.00 meq/g for
ring. The disappearance of peaks at the frequency of the sulphonated polymer. IEC provides an indication

Fig. 2. IR curves for sulphonated and unsulphonated PSEBS.

2648 D. Sangeetha / European Polymer Journal 41 (2005) 2644–2652

Fig. 3. DSC curves of the polymers.

Fig. 4. Thermograms of the polymers.

of the content of acid groups present in a polymer ma- ties for the membranes prepared, along with the values
trix, which are responsible for the conduction of protons for DupontÕs Nafion are quoted in Table 1(a).
and thus is an indirect and reliable approximation of the
proton conductivity. The degree of sulphonation was 3.3. Leach test
also calculated. The proton conductivity of the mem-
branes was found to be excellent in the order of It was observed that, there was not much change in
10
1 S/cm. The values of IEC and protonic conductivi- the conductance value of these ionomer membranes,

Table 1(a)
Comparison of properties of Nafion and PSEBS membrane
Membrane Dry thickness (lm) IEC (meq/g) EW Degree of sulfonation (%) Proton conductivity (S/cm)

Nafion 117 170 0.91 1100 – 0.030
Nafion 115 120 0.91 1100 – 0.077
PSEBS membrane 150 1.59 630 43 0.382
330 1.33 750 36 0.147
 D. Sangeetha / European Polymer Journal 41 (2005) 2644–2652 2649

Table 1(b)
Comparison of properties of Nafion and PSEBS membrane
Membrane Dry thickness (lm) Maximum absorption Uptake of solvent molecules
(wt.%) per SO3H group
Water Methanol Water Methanol

Nafion 117 170 36 85 22 27
Nafion 115 120 36 87 22 28
PSEBS membrane 150 164 192 57 36
330 142 180 59 39

when stored in water for a period of 1 month at room large amount of water, which was followed by only a
temperature. The membrane was tested for conductance gradual raise in absorption towards the saturation point.
and washed, dried and soaked in fresh de-ionized water While, the absorption of methanol was relatively lower
every day. The conductance value was found to be stable than the water absorption at the beginning, it reached
in the same order. The sulphonated polymer membranes higher values towards equilibrium. But, the uptake of
are found to be active enough in conduction and the water molecules per sulphonic group is higher than that
properties of them were not lost even after a period of of the methanol in PSEBS membrane, whereas the up-
1-month storage in water. This confirms that the acidity take of methanol is greater than water in Nafion mem-
is not due to any surface acids or loosely attached acid branes (Table 1(b)). This behaviour may be better
groups and also that there is no loss of active sulphonic explained if the microstructure of the ionomer is investi-
acid groups, attached to the polymers that are responsi- gated. The structure of sulphonated poly(styrene-isobu-
ble for the protonic conductivity. tylene-styrene), a tri block copolymer ionomer was
characterized using small angle X-ray scattering and re-
3.4. Solvent absorption studies vealed a lamellar morphology with a preferred orienta-
tion in the plane of membrane, which measured a
3.4.1. Maximum uptake of solvents proton conductivity much higher than that measured
The water and methanol absorption of the mem- normal to the plane [40].
branes are usually defined in weight percent with respect
to the weight of the dry membrane. At room tempera- 3.4.2. Water content dependence of conductivity
ture, for a membrane of thickness 150 lm, the maximum The existence of water in the membrane greatly influ-
absorption of water and methanol were 164% (by ences the basic properties of the membrane. The absor-
weight) and 192% (by weight) respectively; while it was bance of water by the membrane plays an important role
about 142% and 180% of solvents absorption for a mem- in its conducting phenomena. The water content depen-
brane of 330 lm thickness. This is because of the differ- dence of the membranes on conductivity was studied at
ence in EW values in both the membranes that were room temperature. The conductivity of the dry mem-
prepared. Fig. 5 shows the solvent absorptions of the brane was measured at first. After putting the membrane
membranes studied. The membranes initially absorbed in water, the conductivity was measured continuously at
the required intervals of time. The corresponding in-
crease in the proton conductivity was noted. The values
are tabulated in Table 2. It was found that the conduc-
tance increased gradually along with the increase in the
water content and was almost stable in its order towards
the equilibrium.

3.4.3. Porosity and water/methanol overall uptake

It is observed from the results (Tables 3 and 4) that,
the porosity and the uptake of either water or metha-
nol solvent molecules are higher for the PSEBS iono-
mer membrane than the Nafion 117 membrane after
immersing them in the various concentrated solutions
for 24 h at room temperature. For both the membranes,
in contact with methanol solution, the uptake of metha-
nol molecules (kmethanol) increases with the concentra-
Fig. 5. Solvent absorption curves. tion of methanol solution, which is due to the increase
2650 D. Sangeetha / European Polymer Journal 41 (2005) 2644–2652

Table 2 swelling (porosity, e), which is a weight based quantity

Water content dependence of conductivity of the membrane at increases as the concentration of contacting methanol
room temperature solution is increased, in the two membranes.
Time (min) Thickness (·103 cm) Conductivity In general, the water molecule uptake per sulphonic
(S/cm) acid group (59.38) is greater than the methanol molecule
0 (Dry membrane) 37 5.18 · 10
3 uptake per sulphonic acid group (42.48); in the PSEBS
5 40 3.67 · 10
2 membrane. Hence, it can be concluded that the synthe-
10 42 5.44 · 10
2 sized membranes are less permeable to methanol than
15 44 6.68 · 10
2 water, the condition, which is desirable to decrease the
30 45 1.12 · 10
1 methanol cross-over rate in a DMFC, when compared
45 45 1.16 · 10
1 to a Nafion membrane, which takes up more number
60 45 1.20 · 10
1 of methanol molecules per sulphonic acid group than
120 46 1.22 · 10
1
water molecules.
1440 46 1.22 · 10
1

3.4.4. Water desorption studies

The results are summarized in Tables 5(a) and 5(b). It
Table 3
is well understood from the results, that the membrane
PSEBS membrane porosity and uptake of solution molecules
per sulphonic group at room temperature
can be expected to perform better till the temperature
of 60 C, up to 1 h where it holds some amount of water
Methanol e ktotal kwater kmethanol in it. Above 60 C, where its capacity to withhold water
concentration
molecules, starts decreasing, the performance can also
(mol dm
3)
go down. Hence, humidification becomes mandatory
0.0 0.5640 59.38 59.38 0.0 above 60 C, for the membrane to be active enough to
1.0 0.5643 57.20 54.91 2.29 conduct protons across them. Fig. 6 shows the capacity
2.0 0.5668 55.30 50.88 4.42
of the membranes to withhold water with itself, when
3.0 0.5692 53.56 47.13 6.43
4.0 0.5718 52.04 41.63 8.33
maintained at various temperatures (without humidifica-
5.0 0.5782 51.04 41.12 10.28 tion) over a period of time. The figure clearly indicates
10.0 0.6079 48.51 29.11 19.41 the inability of the membranes to hold water beyond
100% Methanol 0.6833 42.48 0.0 42.48 60 C, whereas below 60 C the membranes are able to
possess certain percentage of water molecules within
them, without external humidification. While the per-
centage of absorption of water by the membranes are
Table 4
shown in Fig. 6, the same in terms of percentage of
Nafion 117 membrane porosity and uptake of solution
desorption i.e., reduction in absorption capacity over a
molecules per sulphonic group at room temperature
period of time at various temperatures are shown in
Methanol e ktotal kwater kmethanol Figs. 7 and 8. It is observed from the figures that humid-
concentration
ification becomes a mandatory to perform efficiently
(mol dm
3)
after 1 h ever for those membranes maintained at tem-
0.0 0.4048 20.76 20.76 0.0 peratures below 60 C.
1.0 0.4131 21.07 20.69 0.38
2.0 0.4233 21.52 20.71 0.81
4.0 0.4396 22.13 20.40 1.73
6.5 0.4571 22.47 19.46 3.01 Table 5(a)
8.0 0.4953 25.31 20.99 4.32 Water desorption (%) of the PSEBS membrane at different
10.0 0.5052 25.11 19.48 5.62 temperatures
Source: Gottesfeld S, Fuller TF, editors. Proc 2nd Intl Symp Time (h) Temperature (C)
PCMFCs, vol. 98-27, 1999. p. 349.
25 30 40 50 60
0 200 188 208 203 180
in the concentration and availability of methanol than 1 49.0 37.0 8.6 8.1 2.6
water molecules. But, the uptake of water molecules 2 11.0 10.5 7.0 6.0 2.4
(kwater) for Nafion 117 membrane remains almost con- 3 10.5 8.1 6.0 5.3 2.2
stant, while there is a decrease in the water uptake of 4 10.6 7.4 5.2 5.2 2.0
PSEBS membrane, which is a generally expected trend. 5 10.6 7.4 4.9 5.0 1.6
Total uptake of both methanol and water molecules 6 10.6 7.4 5.0 4.8 1.6
per sulphonic acid group, ktotal in the PSEBS membrane 7 10.6 7.4 5.0 4.7 1.5
8 10.6 7.3 5.0 4.7 1.5
also shows the same trend as that of kwater. The degree of
 D. Sangeetha / European Polymer Journal 41 (2005) 2644–2652 2651

Table 5(b)
Water desorption (%) of the PSEBS membrane at different
temperatures
Time (min) Temperature (C)
70 80 90 100
0 185 188 185 180
5 104 96 91 7.8
10 408 44 42 2.1
15 19 16 3 0.13
30 3.9 2.3 1.7 0.0
45 2.6 1.2 1.4 0.0
60 1.4 0.8 0.05 0.0
120 0.9 0.5 0.0 0.0
180 0.3 0.2 0.0 0.0
240 0.2 0.0 0.0 0.0
300 0.0 0.0 0.0 0.0 Fig. 8. Desorption isotherms (II).

4. Conclusion

Sulphonated polystyrene-poly(ethylene–butylene)-
polystyrene tri block polymer was prepared from a
low cost material by sulphonating the styrene blocks
of the polymer and membranes of various thickness
were prepared from the sulphonated polymer by cast-
ing method. The proton conductivities of these mem-
branes were found to be excellent in the order of
10
1 S/cm. FTIR spectra confirmed the sulphonation
of the polymer. DSC and TGA analyses showed that
the thermal stability of the polymer decreases and
the Tg of the polymer increase due to sulphonation.
Solvent absorption properties of membranes were stud-
ied extensively. The uptake of water molecules per sul-
phonic acid group is higher than the uptake of
methanol molecules per sulphonic acid group in the
Fig. 6. Weight absorption curves.
ionomer chain. Desorption studies were also carried
out for the membranes maintained at various tempera-
tures.
In direct methanol fuel cell (DMFC), the high meth-
anol permeability in Proton exchange membrane lead to
lower cell efficiencies. Hence an attempt was made to de-
velop a new proton exchange membrane with high pro-
ton conductivities in general, and to increase DMFC
efficiencies. The focus of the investigation was to analyze
the solvent uptake properties, since one of the major
obstacles hindering the use of Nafion membranes in
DMFC is the methanol cross-over to the cathode and
poisoning of the cathode catalyst, thereby reducing the
cell efficiency. Hence, these membranes that are less per-
meable to methanol than water, are expected to perform
better in such fuel cells. Finally, the desorption results
reveals that the humidification of membrane in the fuel
cell assembly becomes a necessity to maintain the water
content and subsequently the conductivity, especially at
temperatures higher than 60 C and for an efficient and
Fig. 7. Desorption isotherms (I). continuous performance of the cell.
2652 D. Sangeetha / European Polymer Journal 41 (2005) 2644–2652

Further work is required to understand the influence [20] Banaszek M, Whitmore MD. Macromolecules
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[22] Mani S, Weiss RA, Williams CE, Hahn SF. Polym Mat Sci
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Eng 1994;71:565.
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