Journal of Membrane Science 225 (2003) 63–76

Synthesis and characterization of proton conducting

polymer membranes for fuel cells
B. Smitha, S. Sridhar, A.A. Khan∗
Membrane Separations Group, Chemical Engineering Division, Indian Institute of Chemical Technology,1 Hyderabad 500 007, India
Received 15 January 2003; received in revised form 15 July 2003; accepted 18 July 2003

Abstract
Commercial polymers with aryl backbones such as polystyrene (PS), polycarbonate (PC), polysulfone (PSf) and poly
(phenylene oxide) (PPO) were sulfonated using suitable reagents, and assessed for their potential to serve as proton exchange
membranes (PEM) in fuel cells (FCs). The membranes thus synthesized were characterized by Fourier transform infra-red
(FTIR) and 1 H NMR to verify sulfonation and to identify the sites available for proton conduction. Differential scanning
calorimetry (DSC) and thermogravimetric analysis (TGA) studies were carried out to investigate the thermal stability of the
sulfonated membranes. Surface morphology and tensile strength were evaluated by scanning electron microscopy (SEM) and
UTM, respectively. Sorption experiments were conducted to observe the interaction of sulfonated polymers with water and
methanol. The ion exchange capacity (IEC), which is a measure of proton conductivity, and the degree of substitution (DS) were
evaluated and found to be comparable with the commercially available Nafion membranes. Sulfonated polycarbonate (SPC)
was found to possess all the requisite properties of a PEM; namely, high IEC (0.57 meq./g), tensile strength (157 N/mm2 ) and
thermal stability (Tg = 120 ◦ C) besides low affinity towards methanol (%sorption = 2.97). The study reveals the possibility of
developing inexpensive and sturdy fuel cell membranes, which could provide attractive alternatives to substitute the expensive
commercially available membranes.
© 2003 Elsevier B.V. All rights reserved.
Keywords: Polymer electrolyte membranes; Aryl backbone; Ion exchange capacity; Degree of substitution; Membrane characterization

1. Introduction

Fuel cells (FCs) have emerged strongly as a viable

Abbreviations: PEM, polymer electrolyte membrane; PPO, poly
(phenylene oxide); PSf, polysulfone; PS, polystyrene; PC, poly-
carbonate; FTIR, Fourier transform infra-red; NMR, nuclear mag-
netic resonance spectroscopy; SEM, scanning electron microscopy;
DSC, disc scanning calorimetry; TGA, thermogravimetric analy-
sis; SPPO, sulfonated PPO; SPSf, sulfonated PSf; SPS, sulfonated
PS; SPC, sulfonated PC; IEC, ion exchange capacity; DS, degree
of substitution; DMAc, N,N-dimethyl acetamide
∗ Corresponding author. Tel.: +91-40-719-3139/3626;
alternative source of power owing to their high-energy
efficiency and eco-friendly nature [1,2]. The proton
exchange membrane (PEM) in fuel cells have been
well established for over five decades and are suc-
cessfully commercialized as electrical power sources
in spacecrafts and submarines [3]. During the last
decade the compatibility of PEM-FCs as power source
in mass production of automobiles and portable elec-

fax: +91-40-719-0387/0757.
trical devices, is well fathomed [1]. This has lead to
E-mail address: aakhan iict@rediffmail.com (A.A. Khan). an increasing interest in materials being used as elec-
1 IICT Communication No. 030613. trolytes. Currently, the choice is confined to hydrated

0376-7388/$ – see front matter © 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0376-7388(03)00343-0
64 B. Smitha et al. / Journal of Membrane Science 225 (2003) 63–76
perfluorosulfonic polymers such as Nafion [4]. The
perfluorosulfonic acid membranes cost US$ 800 m−2
and the power generated costs approximate to US$
150 kW−1 [4]. Since the technical feasibility of fuel
cells has been to a large extent successfully demon-
strated, the industry is currently engaged in field trials,
lowering costs and determining manufacturing strate-
gies [5]. Hence, despite the superior performance of
the membranes currently used in fuel cells, their inher-
ently high cost of production limits their usage in fu-
ture mass-produced appliances including automobiles.
From the application point of view, any membrane
even the one without fluorine chemistry, but hav-
ing high temperature resistance, greater mechanical
strength and high proton conductivity would be useful.
Currently there is an increasing interest in a va-
riety of polymers having fluorinated alkyl and aryl
backbones to serve as suitable membranes for fuel
cell applications [6]. Sulfonation is a powerful and
versatile process, which can be used to simultane-
ously render these polymers proton conductive as
well as hydrophilic in nature. Sulfonated polymers
can be prepared in the form of free acid (–SO3 H),
a salt (e.g. –SO3 − Na+ ) or an ester (–SO3 R) [7].
The degree of sulfonation can be controlled as de-
sired. The polymers can be sulfonated in the initial
stages of synthesis or can be sulfonated in their final
form. Any of the homopolymers, random copolymers
and block and graft copolymers containing aromatic
rings or double bonds are suitable as building blocks
for this application. Extensive sulfonation leads to
water-soluble polymers, which find use as thickeners
and flocculants. Sulfonation improves the dye-ability
of propylenestyrene copolymer fibers [8]. The sodium
salt of sulfonated butyl rubber is reportedly stronger
than the unsulfonated polymer [9,10]. Sulfonated
polyesters and polyimides are also mentioned in the
literature [11–13]. Sulfonated polysulfone (SPSf)
membranes are reported to be useful in desalination
applications [14,15].
Polysulfone (PSf) has been sulfonated [7] using
sulfur trioxide–triethyl phosphate complex as sul-
fonating agent and the effect of sulfonation on the
glass transition temperature, water absorption and gas
permeability was studied. The synthesis of sulfonated
poly (phenylene oxide) (SPPO) has been investigated
[16] and the effects of catalyst concentration, solvent
and kinetics of sulfonation have been reported.
In the present study, inexpensive and abundantly
available commercial polymers namely polycarbonate
and polystyrene (PS) have been investigated after sul-
fonation for their resistance to high-temperature and
chemicals. Poly (phenylene oxide) (PPO) and polysul-
fone were also sulfonated as these are polymers with
rigid aryl backbones and completely hydrophobic in
nature [17]. These polymers upon suitable structural
modifications tend to exhibit a number of desirable
properties including high ionic conductivity, good
mechanical strength and reasonably low affinity to
methanol and water. This work is therefore an attempt
to synthesize sulfonated membranes, with hydrophilic
regions around the cluster of side chains in a generally
hydrophobic polymer for promoting proton conduc-
tivity. This modification manifests itself in many ways
such as thermal transitional behavior, mechanical
properties, morphology, and above all the crucial prop-
erty in the context of fuel cells namely ion exchange
capacity. Some of the polymers tested in the study, i.e.
PPO, PSf and PS have been sulfonated earlier and eval-
uated for their ability to behave as solid polymer elec-
trolytes in fuel cells but extensive characterization by
different methods has been lacking which is what this
paper aims to report. Moreover, there is very little lit-
erature on feasibility of using alternatives such as sul-
fonated polycarbonate (SPC) for fuel cell applications.
2. Experimental
2.1. Materials
Poly (phenylene oxide) was synthesized in a sim-
ilar manner to that described in the literature [18].
Polysulfone, polycarbonate and polystyrene of num-
ber average molecular weight of 22,000, 64,000 and
430,000, respectively, were purchased from Aldrich.
Chloroform, 1,2-dichloroethane, acetic anhydride, sul-
furic acid and chlorosulfonic acid of AR grade, were
purchased from S.D. Fine Chem. Ltd., Mumbai.
2.2. Sulfonation of polymers
2.2.1. Choice of sulfonating agent
Three different reagents, viz. sulfuric acid, acetyl
sulfate and chlorosulfonic acid were used to sulfonate
the four polymers used in the study. The criteria for
 B. Smitha et al. / Journal of Membrane Science 225 (2003) 63–76
selection of the best reagent for a specific polymer
was based on its compatibility with polymer and film
forming property besides the mechanical strength of
the sulfonated polymer.
• Sulfuric acid: Sulfonation was done with concen-
trated sulfuric acid (98%) as per the procedure re-
ported in the literature [19]. Despite the addition
of small quantities of acid, it was observed that the
polymer so obtained dissolved completely in water.
Excess of the acid resulted in the degradation of the
polymer which is undesirable. The degree of sul-
fonation could not be controlled and hence sulfuric
acid was found unsuitable as sulfonating agent.
• Chlorosulfonic acid: PPO and PSf were sulfonated
by this reagent. As the extent of sulfonation could be
controlled, it was observed that the resultant poly-
mers swelled in water but did not dissolve com-
pletely. The mechanical strength and film forming
capabilities of the polymer thus formed were rea-
sonably good. PC and PS could not be sulfonated
using this sulfonating agent as the polymer pre-
cipitated as such without undergoing any change.
This was confirmed by Fourier transform infra-red
(FTIR).
• Acetyl sulfate: It is reported that a homogenous dis-
tribution of sulfonic acid groups in the resultant
polymer is obtained when PS was sulfonated using
this reagent [12]. Apart from PS, PC too reacted
readily with acetyl sulfate and the properties of re-
sultant product are encouraging. However, PPO and
PSf could not be sulfonated using this method be-
cause of the lack of their compatibility with the
reagent.
2.2.2. Sulfonation of poly (phenylene oxide)
Sulfonation was carried out in a chloroform solvent
system at ambient conditions using chlorosulfonic
acid as the sulfonating agent as described by Plum-
mer et al. [20]. Prior to the sulfonation step, the small
quantity of sulfonable material (ethanol and water)
in chloroform, used as a solvent for PPO, was deter-
mined and neutralized with chlorosulfonic acid. Ten
grams of PPO was then added to 100 ml of neutral-
ized chloroform, in a three-neck reaction flask, and
dissolved by stirring for about 30 min at room temper-
ature to form 3–6 wt.% solution. A 5% (v/v) solution
of chlorosulfonic acid in 100 ml of chloroform was
65
transferred into a dropper and gradually added to the
PPO solution over a period of 20 min while stirring
the solution vigorously at 25 ◦ C. Special precautions
had to be taken to carry out the reaction involving
the usage of chlorosulfonic acid. The precipitated
polymer, i.e. sulfonated PPO (SPPO), dark brown in
color, was washed with distilled water and allowed to
dry in air for 24 h at room temperature [18].
2.2.3. Sulfonation of polysulfone
Polysulfone was sulfonated on similar lines as that
of PPO.
2.2.4. Sulfonation of polystyrene
Sulfonated polystyrene (SPS) was prepared by us-
ing acetyl sulfate as the sulfonating agent [21] which
was freshly prepared by mixing 15.3 ml of acetic
anhydride with 5.6 ml of sulfuric acid in 79 ml of
1,2-dichloroethane. The desired quantity of acetyl
sulfate solution was added to a reaction flask con-
taining a solution of 20.8 g of polystyrene in 98 ml
of 1,2-dichloroethane. The sulfonation reaction was
allowed to proceed for 1 h at 50 ◦ C and was then ter-
minated by adding methanol. The resulting sulfonated
polystyrene was isolated by introducing steam. The
polymer was then collected and recovered by filtration.
2.2.5. Sulfonation of polycarbonate
Polycarbonate was sulfonated in a manner analo-
gous to that of polystyrene.
2.2.6. Effect of concentration of sulfonating agent
Experiments were carried out by adding varying
quantities of sulfonating agents to the same quantity
of the polymer. The effect is best illustrated by citing
examples of sulfonation of PPO and PSf with chloro-
sulfonic acid.
(a) 2.5% of chlorosulfonic acid: Addition of entire
quantity did not result in the formation of any pre-
cipitate and hence the polymer had to be precip-
itated in methanol. The polymer so obtained did
not exhibit film forming property as it was not sol-
uble in any solvent after drying.
(b) 5% of chlorosulfonic acid: Addition of 70–75 ml
of chlorosulfonic acid and chloroform mixture into
the reaction vessel resulted in the precipitation
of the polymer. The sulfonated polymer did not
66 B. Smitha et al. / Journal of Membrane Science 225 (2003) 63–76
exhibit excessive swelling and hence membranes
cast out of this method were chosen for character-
ization.
(c) 10% of chlorosulfonic acid: In this case, it was
observed that addition of 25–35 ml of the mixture
resulted in the precipitation of the polymer. The
polymer obtained was in the degraded state and
the membrane so formed was completely soluble
in water.
Thus, based on the trials, addition of 5% of chloro-
sulfonic acid to chloroform was chosen as the opti-
mum quantity of sulfonating agent.
2.3. Preparation of membranes
Membranes synthesized for the study were prepared
by solution casting and solvent evaporation technique.
Approximately 5 wt.% of SPPO in DMAc, 15 wt.%
of SPSf in N,N-dimethyl formamide and 12 wt.% of
SPC in 1,4-dioxane were dissolved in the respective
solvents.
A solution (32 g/l) of SPS in toluene/n-butanol mix-
ture (7:3, v/v) is prepared, filtered and spread on a
Fig. 1. Chemical structure of: (a) SPSf, (b) SPC, (c) SPS and (d) SPPO.
clean glass plate to obtain dense membranes. The cast
films were evaporated to dryness in open air at room
temperature (30–35 ◦ C) and were later vacuum dried
for a period of 12 h at ambient temperature to expel
traces of solvent. Membranes were also prepared from
respective unsulfonated polymers, using a similar pro-
cedure, for comparison of various characteristics.
Fig. 1 shows the chemical structures of the sul-
fonated membranes prepared in the study.
2.4. FTIR studies
The FTIR spectra of unsulfonated and sulfonated
membranes were scanned using Nicolet-740, Perkin-
Elmer-283B FTIR Spectrometer. These spectra are
shown in Figs. 2 and 3.
2.5. NMR studies
The 1 H NMR spectra of unsulfonated and sul-
fonated membranes were scanned to detect the occur-
rence of sulfonation. The solvent used to dissolve the
polymer samples was deuterated chloroform (CDCl3 ).
Observed spectrum is recorded in Fig. 4.
 B. Smitha et al. / Journal of Membrane Science 225 (2003) 63–76 67

Fig. 2. FTIR spectra of: (a) polystyrene and (b) sulfonated polystyrene.

2.6. Thermal analysis 700 ◦ C heated at 10 ◦ C/min in nitrogen gas flushed at

2.6.1. DSC studies
The differential scanning calorimetry (DSC) spectra
of sulfonated and unsulfonated polymers were obtai-
ned on Perkin-Elmer DSC Model 7. Measurements
were performed over the temperature range of
30–200 ◦ C at the heating rate of 5 ◦ C/min in herme-
tically sealed aluminium pans. Membrane samples
were allowed to attain steady state with the solvents
and the sample pan conditioned in the instrument
before running the experiment. Results are shown in
Figs. 5 and 6.
2.6.2. TGA
Thermal stability of the polymer films was exam-
ined, using Seiko 220TG/DTA analyzer, from 25 to
200 ml/min. The samples were subjected to thermo-
gravimetric analysis (TGA) both before and after sul-
fonation to determine the decomposition temperatures.
Results are shown in Fig. 7.
2.7. Determination of the ion exchange capacity
and degree of substitution
The ion exchange capacity (IEC) indicates the
number of milli-equivalents of ions in 1 g of the dry
polymer. The degree of substitution (DS) indicates
the average number of sulfonic groups present in the
sulfonated polymer. To determine the degree of sub-
stitution by acid groups, the sulfonated membranes
and unsulfonated specimens of similar weight were
68 B. Smitha et al. / Journal of Membrane Science 225 (2003) 63–76

Fig. 3. FTIR spectra of: (a) polycarbonate and (b) sulfonated polycarbonate.

soaked in 50 ml of 0.01 N sodium hydroxide solution Relationship between DS and IEC is

for 12 h at ambient temperature. Then, 10 ml of the
120 × IEC
solution was titrated with 0.01 N sulfuric acid [5]. The DS =
sample was regenerated with 1 M hydrochloric acid, 1000 + 120 × IEC − 200 × IEC
washed free of acid with water and dried to a constant
weight. The IEC was calculated according to: 2.8. Swelling

B − P × 0.01 × 5 In order to determine their interaction, weighed

IEC =
m samples of circular pieces of sulfonated polymer films
where IEC is the ion exchange capacity (meq./g),
B the sulfuric acid used to neutralize blind sample
soaked in NaOH (ml), P the sulfuric acid used to
neutralize the sulfonated membranes soaked in NaOH
(ml), 0.01 the normality of the sulfuric acid, 5 the
factor corresponding to the ratio of the amount of
NaOH taken to dissolve the polymer to the amount
used for titration, and m the sample mass (g).
(3 cm diameter) were soaked in water and methanol.
The films were taken out after different soaking pe-
riods and quickly weighed after carefully wiping out
excess water/methanol to estimate the amount ab-
sorbed at the particular time “t”. The film was then
quickly placed back in the solvent. The process was
repeated until the films attained steady state as in-
dicated by constant weight after a certain period of
 B. Smitha et al. / Journal of Membrane Science 225 (2003) 63–76 69

Fig. 4. 1 H NMR spectra of: (a) polystyrene and (b) sulfonated polystyrene.

soaking time. The degree of swelling was calculated between the grips of the testing machine. The grip
from: length was 5 cm and the speed of testing was set at the
Ms − Md rate of 12.5 mm/min. Tensile strength was calculated
swelling (%) = × 100 using:
Md
where Ms is the mass of the swollen polymer in g and max load
tensile strength (N/mm2 ) = .
Md the mass of the dry polymer in g. cross-sectional area

2.9. Mechanical properties 2.10. Scanning electron microscopy

The equipment used for carrying out the test was
Universal Testing Machine (Shimadzu make, model
AGS-10kNG) with an operating head load of 5 kN.
Cross-sectional area of the sample of known width and
thickness were calculated. The films were then placed
The films were thoroughly dried and the surface
morphology was studied by scanning electron mi-
croscopy (SEM) using a Hitachi S2150 microscope.
The SEM images for polysulfone and polystyrene
before and after sulfonation are shown in Fig. 8.
70 B. Smitha et al. / Journal of Membrane Science 225 (2003) 63–76

3. Results and discussion

The chemical structures of the sulfonated polymers

prepared in this study are presented in Fig. 1. The
membranes made from the polymers were charac-
terized extensively for their thermal stability, tensile
strength, swelling and finally for IEC.

3.1. FTIR analysis

Two sets of FTIR spectra comparing sulfonated

Fig. 5. DSC spectra of: (a) polycarbonate and (b) sulfonated
polycarbonate.
Fig. 6. DSC spectra of: (a) polystyrene and (b) sulfonated
polystyrene.
and unsulfonated films pertaining to polystyrene and
polycarbonate are presented in Figs. 2 and 3, respec-
tively, and the spectra relating to polysulfone and
poly (phenylene oxide) are only presented in the text
in order to save the manuscript space. Referring to
Fig. 2 it can be seen that the sharp peaks at 700
and 780 cm−1 in unsulfonated polystyrene are due
to –C–H out of plane deformation which represent
mono substitution. The disappearance of these peaks
after sulfonation followed by the occurrence of a new
peak at 520 cm−1 representing para substitution is
indicative of the attachment of sulfonic acid groups
at para position. The peak identified in the spectra
at 1360 cm−1 is due to the asymmetric stretching
of S=O bond. The symmetric vibration of this bond
produces the characteristic split band of absorbance
at 1150–1185 cm−1 . There was no significant change
observed in the peaks at 2925 and 3000 cm−1 , which
represent C–C and C–H bond, respectively.
Sulfonated polycarbonate spectra in Fig. 3 shows
sharp peaks at 1160 and 1340 cm−1 which are not
present in the broad band peaks at 1150–1220 cm−1
observed for unmodified polycarbonate. As in the case
of sulfonated polystyrene, the peak at 1360 cm−1 iden-
tified in the spectra is due to the asymmetric stretching
of S=O bond and the symmetric vibration of this bond
produces the characteristic split band of absorbance at
1150–1185 cm−1 .
Sulfonated polysulfone shows a peak represent-
ing a broad H-bonded O–H stretch in the range
of 1175–1150 cm−1 . The asymmetric stretching of
S=O bond occurs at 1350–1340 cm−1 with an O–H
stretching around 1165–1150 cm−1 .
Spectra of sulfonated PPO showed the aromatic
group at 1600 and 1490 cm−1 , sulfonic acid at 1070
and 675 cm−1 and S=O stretching vibration at 1369
and 1163 cm−1 .
 B. Smitha et al. / Journal of Membrane Science 225 (2003) 63–76
Fig. 7. TGA of: (a) sulfonated PPO and (b) sulfonated polystyrene.
Thus, the results of FTIR analysis clearly prove the
occurrence of sulfonation by the presence of sulfonate
groups after the reaction in all the four polymers.
3.2. NMR analysis
1 H NMR spectra before and after sulfonation is pre-
sented for polystyrene only (Fig. 4) whereas the in-
terpretation is reported in case of all the rest of the
polymers. In the case of sulfonated polystyrene, no
significant change is noticed in the signals at 7.3, 6.6
and 7 ppm. A hump between 5 and 6 ppm indicates
the presence of sulfonic acid linkage on the aromatic
benzene ring.
The aromatic portion of the 1 H NMR spectra of
sulfonated polycarbonate is diminished on account of
sulfonation. This depicts replacement of aromatic pro-
tons by sulfonic acid groups. New signals at 3.2, 3.4
and 3.6 ppm portray the change of field around the
protons on the methyl groups.
A shift in the range of protons, from 8 to 8.3 ppm
next to the sulfone bridge of the polysulfone, is ob-
71
served in the case of sulfonated polysulfone. This is
due to the stronger electron attracting force of the sul-
fonic acid group. Similar indications of sulfonation
were observed in the 1 H NMR spectra of sulfonated
PPO.
3.3. Tensile strength and elongation
The tensile strength at break of the polymers before
and after sulfonation is given in Table 1. From the re-
sults, it can be observed that there is a decrease in the
tensile strength and elongation of all the polymers af-
ter sulfonation. This reduction may be attributed to the
degree of substitution. Sulfonation causes the polymer
matrix to expand. This expansion permits an increase
in the free volume thereby increasing the chain move-
ments which makes the plastic material softer and
flexible. This greater chain movement implies that the
material changes partially from glassy state (hard and
brittle) to rubbery state (flexible and soft), thereby
causing a reduction in the tensile strength at break
and a corresponding reduction in the elongation [23].
72 B. Smitha et al. / Journal of Membrane Science 225 (2003) 63–76

Fig. 8. SEM picture of: (a) PS, (b) SPS, (c) PSf and (d) SPSf.

3.4. Thermal analysis
3.4.1. DSC spectra
The DSC spectra are shown in Figs. 5 and 6. In the
case of polystyrene, the Tg value after sulfonation is re-
duced from 87 to 30 ◦ C, polycarbonate shows a reduc-
tion from 147 to 120 ◦ C, poly (phenylene oxide) from
145 to 114 ◦ C and polysulfone from 185 to 140 ◦ C.
The unneutralized free acid forms (–SO3 H) of all the
sulfonated polymers used in the study display a signif-
icantly lower Tg than the unsulfonated ones. This may
be ascribed to the structural changes introduced into
 B. Smitha et al. / Journal of Membrane Science 225 (2003) 63–76
Table 1
Tensile strength and elongation of all the polymers used in the
study
Polymer Tensile strength (N/mm2 ) Elongation (%)
SPPO 146.666 5.671
PPO 176.864 13.456
SPSf 138.422 3.732
PSf 191.822 10.783
SPS 119.666 2.648
PS 140.321 8.965
SPC 157.277 7.952
PC 182.333 19.734
the polymer on account of sulfonation. The higher the
degree of substitution, the greater is the free volume
of a sulfonated product membrane enabling a change
in the state of polymer from more amorphous to more
crystalline resulting in the reduction of the glass tran-
sition temperature. This effect is illustrated clearly by
the DSC spectra for polycarbonate and polystyrene
before and after sulfonation as shown in Figs. 5 and 6.
3.4.2. Thermal stability by thermogravimetric
analysis
Fig. 7 shows the thermogravimetric analysis spec-
tra of SPPO films prepared by using DMAc. The films
were dried at room temperature for several days and,
before TGA analysis, the films were exposed to air
at atmospheric conditions. Three weight loss stages at
60–120, 220–270 and 420–460 ◦ C followed by the fi-
nal decomposition of polymer can be distinguished in
the figure. The final decomposition begins at around
460 ◦ C. The locations of the weight loss stages ob-
served here are almost similar to those reported by
Gilbert et al. [22]. For the films being exposed to air
before subjecting to TGA, the weight loss in the first,
second and third stage can be attributed, respectively,
to the loss of moisture absorbed from air, the decompo-
sition of sulfonic groups and the splitting of the main
chains before the final decomposition of the polymer.
In the case of SPC, the three weight loss stages were
found at 70–140, 260–410 and 470–500 ◦ C and the
final decomposition occurred at around 510 ◦ C. The
causes for the weight loss are similar to the ones stated
earlier.
Sulfonated polysulfone again shows three weight
loss stages at 110–140, 195–250 and 325–360 ◦ C. Fi-
nal decomposition is observed at around 510 ◦ C.
73
Sulfonated polystyrene (Fig. 7) behaved differently
with only one weight loss stage at 465–510 ◦ C. Weight
loss at this stage may be due to the splitting of the
main chains or it could also be related to the evapo-
ration of residual solvent. Though the boiling point of
the solvent is much less than the temperature in the
weight loss zone, the fact that the polymer is in a rub-
bery state cannot be overlooked. An increase in free
volume in the rubbery state and the excessive sliding
of polymer chains one upon another with an increase
in temperature would enhance evaporation of residual
solvent entrapped in the polymer at glassy state result-
ing in weight loss at a temperature much higher than
its boiling point.
3.5. Water and methanol sorption
Table 2 shows the equilibrium percentage sorption
of water and methanol in the normal and sulfonated
polymers. Water sorption depends on the extent of
sulfonation, hence higher the degree of substitution,
greater the water uptake. From the table it can be
observed that the water sorption prior to sulfonation,
in the unmodified hydrophobic polymers was low and
varied from as low a value as 0.01% in PSf to 0.27
in PPO. After sulfonation, the values obtained were
considerably high and are in the range of 10.8–17.2%
indicating the presence of hydrophilic sites within the
hydrophobic matrix. The swelling ratio for sulfonated
polycarbonate was 1.17 followed by sulfonated poly
(phenylene oxide) with 1.1.4 and sulfonated polysul-
fone with 1.138. An earlier study reported a swelling
ratio of 1.245 at 0.5 DS for sulfonated polysulfone
[7] which is comparable to the present case. For
sulfonated polysulfone which are ideal for fuel cell
membranes since excessive swelling can cause rup-
ture of membranes losses of hydrogen/methanol by
Table 2
Sorption values for water and methanol in the sulfonated polymers
Polymer Water sorption (%) Methanol sorption (%)
BSa ASb BS AS
SPPO 0.27 14.37 1.12 1.14
SPSf 0.01 13.84 0.23 4.62
SPS 0.16 10.78 0.44 1.08
SPC 0.13 17.21 0.98 2.97
a Before sulfonation (BS).
b After sulfonation (AS).
74 B. Smitha et al. / Journal of Membrane Science 225 (2003) 63–76
permeation through the barrier, and difficulties in gas
flow control through the fuel cell manifold/channels
whereas very low swelling (<1.05) results in inef-
ficient proton transfer rates. Though the methanol
sorption values increased considerably after sulfona-
tion for polycarbonate from 0.98 to 2.975% and PSf
from 0.23 to 4.62% compared to PPO and PS the
range for degree of swelling was still low enough
(1.01–1.046) to prevent excessive losses of methanol
through the membrane in DMFC.
3.6. SEM
Fig. 8 shows the surface morphology of polystyrene
and polysulfone before and after sulfonation. The
enhancement in the size of pores after sulfonation of
the membranes can be observed clearly. Further, there
appears to be a uniform distribution of pores through-
out the membranes after sulfonation. The number of
pores per sq.cm area for sulfonated polystyrene and
sulfonated polysulfone ranges from 2 to 3 and 3 to
4 millions, respectively. The pore size in sulfonated
polystyrene and sulfonated polysulfone are 2.5 and
1.9 ␮m, respectively. Their uniform and adequate
size and even distribution ensure a desirable and ef-
ficient conductivity of protons besides a sufficiently
large interfacial area between the hydrophobic and
hydrophilic interface [1].
3.7. IEC and DS
Ion exchange capacity provides an indication of the
content of acid groups present in a polymer matrix [5]
which are responsible for the conduction of protons
and thus is an indirect and reliable approximation of
the proton conductivity. Results are based on the sam-
ple calculations reported in Appendix A [5]. The IEC
and DS values of all the polymers used for the study
are tabulated in Table 3. It can be seen that the IEC
Table 3
IEC and DS values of polymers prepared for the study
Polymer IFC (meq./g)
SPS 0.2799
SPSf 0.3976
SPPO 0.4217
SPC 0.5798
value for SPC (0.5798) is highest and SPS (0.2799)
is the lowest. SPPO and SPSf showed moderate IEC
values.
Sulfonated polycarbonate appears to be a promising
alternative proton exchange membrane since it shows
a greater IEC value. Unlike Nafion which is expen-
sive, polycarbonate polymer is inexpensive and can
be synthesized and sulfonated on a commercial scale
[13]. Characterization of SPC by UTM shows rea-
sonable tensile strength (157 N/mm2 ) and flexibility
(percentage elongation ∼8). Additionally, the Tg of
sulfonated polycarbonate is found to be much higher
than the operating temperature range (80 ◦ C) of a PEM
fuel cell [24]. The crucial second stage weight loss
at 260–410 ◦ C caused by decomposition of sulfonic
groups and depicted by TGA, proves the thermal sta-
bility of SPC.
4. Conclusions
Introduction of hydrophilic sites in hydrophobic
polymers with rigid aryl backbones appears to pro-
duce promising electrolyte membranes for fuel cell
applications. Three of the four membranes tested,
except SPS, showed IEC values and other essential
properties comparable to commercial Nafion mem-
brane. SPC appears to be a viable alternative owing
to its low cost, high IEC and DS, good mechanical
and thermal stability and low sorption for methanol.
SPS showed a steep fall in glass transition tempera-
ture to a level which does not comply with requisite
operating conditions in PEM fuel cells. However,
this drawback can be overcome by crosslinking or
copolymerization with other suitable polymers. All
the sulfonating agents produced membranes capable
of proton conduction but the best reagent–polymer
combinations appeared to be chlorosulfonic acid
for PPO and PSf and acetyl sulfate for PS and PC.
Increase in concentration of sulfonating agents in-
creased the IEC and DS of the polymers but can-
not ensure uniform distribution of sulfonic groups
within the polymer matrix. It may yield completely
DS soluble membranes or polymer degradation may be
0.03436 observed in some cases. Thus there is a general
0.04926 trend of reduction in Tg and mechanical strength.
0.05237
Extensive sulfonation leads to proportional increase
0.07296
in interaction with water and ultimately at high
 B. Smitha et al. / Journal of Membrane Science 225 (2003) 63–76
levels of sulfonation the polymer is soluble in wa-
ter. This is unacceptable for any proton exchange
membrane as the fuel cell conditions demand a
level of humidity to promote proton conduction and
suitable modification in polymer structure are war-
ranted.
Acknowledgements
The authors would like to thank Council of
Scientific and Industrial Research, India, for funding
the Fuel Cell Project (ES/P 81-1-03, EMR Head)
Dr. Sridhar, Ms. Dhanuja, Ms. Bhavani, Membrane
Separations Lab, Mr. Sai Babu, Ms. K. Uma Gaya-
tri, Pheromones Lab and Mr. Tajuddin of Chemical
Engineering Division for membrane characterization.
The consistent support and encouragement of Dr.
M. Ramakrishna and Dr. K. Babu Rao of Chemical
Engineering Division is gratefully acknowledged.
Nomenclature
Tg glass transition temperature
Appendix A. Calculations DS and IEC [5]
Consider the case of sulfonated polystyrene:
• Initial conditions:
◦ Mass of dry sulfonated polystyrene = 0.01429 g
◦ Normality of H2 SO4 = 0.01 N (N1 )
◦ Normality of NaOH = 0.01 N (N2 )
• After 12 h:
◦ Blank titration = 7.0 ml
◦ Sample titration = 6.2 ml
◦ Volume of NaOH neutralized = 10 ml
The ion exchange capacity of the sulfonated mem-
brane is calculated as follows:
(blank titration − sample titration)
× normality × 5
IEC =
membrane weight
(7 − 6.2) × 0.01 × 5
= = 0.2799
0.1429
75
The degree of substitution can be calculated by the
formula:
120 × IEC
DS = = 0.03436
1000 + 120 × IEC − 200 × IEC
IEC and DS values for sulfonated polycarbonate,
polysulfone and poly (phenylene oxide) were calcu-
lated on the same lines.
References
[1] K.D. Kreuer, On the development of proton conducting
polymer membranes for hydrogen and methanol fuel cells, J.
Membr. Sci. 185 (2001) 29–39.
[2] A.J. Appleby, F.R. Foulkes, Fuel Cell Handbook, Van
Nostrand Reinhold, New York, 1989.
[3] J. Larminie, A. Dicks, Fuel Cell System Explained, Wiley,
West Sussex, 2000.
[4] W. Becker, G. Schmidt-Naake, Proton exchange membranes
by irradiation grafting of styrene onto FEP and ETFE:
influences of the crosslinker N,N-methylene-bis-acrylamide,
Chem. Eng. Technol. 25 (2002) 364–370.
[5] J.St. Pierre, D.P. Wilkinson, Fuel cells: new, efficient and
cleaner power source, AIChE J. 47 (1998) 1482–1486.
[6] R.J. Bellows, M.Y. Lin, M. Arif, A.K. Thompson, D.
Jacobson, Neutral imaging technique for in situ measurement
of water transport gradients within Nafion in polymer
electrolyte fuel cell, J. Electrochem. Soc. 146 (3) (1999)
1099–1103.
[7] A. Noshay, L.M. Robenson, Sulfonated polysulfone, J. Appl.
Polym. Sci. 20 (1976) 1885–1903.
[8] C. Lopatin, H.A. Newey, Am. Chem. Soc., Div. Polym.
Chem., Polym. Prepr. 12 (2) (1971) 230.
[9] N.H. Canter, Ger. Offen. 1 (915) (1969) 236.
[10] C.P.O. Farrell, G.E. Serniuk, US Patent No. 3,836,511
(1974).
[11] J. Veno, M. Watanabe, Y. Tanaka, Japanese Patent No. 24,998
(1968).
[12] C.J. Kibler, G.R. Lappin, US Patent No. 3,734,874
(1973).
[13] R. Salle, B. Sillion, French Patent No. 2,212,356 (1974).
[14] J.P. Quentin, US Patent No. 3,709,841 (1974).
[15] J. Bourganel, US Patent No. 3,855,122 (1974).
[16] R.Y.M. Huang, J.J. Kim, Synthesis and transport properties
of thin film composite membranes, J. Appl. Polym. Sci. 29
(1984) 4017–4027.
[17] Mitchell, Will, Fuel Cells, vol. 1, Academic Press, New York,
1963.
[18] B. Kruczek, T. Matsurra, Development and characterization
of homogeneous membranes to form high molecular weight
SPPO, J. Membr. Sci. 146 (1998) 263–275.
[19] U. Pedretti, A. Gandini, A. Roggero, C. Sisto, C. Valentini,
A. Stopponi, US Patent No. 5,169,416 (1992).
[20] C.W. Plummer, G. Kimura, A.B. LaConti, Development of
Sulfonated Polyphenylene Oxide Membranes for Reverse
Osmosis, General Electric Co., Lynn, MA, 1970.
76 B. Smitha et al. / Journal of Membrane Science 225 (2003) 63–76

[21] N. Carretta, V. Tricoli, F. Picchion, Ionomeric membranes
based on partially sulfonated poly(styrene), J. Membr. Sci.
166 (2000) 189–197.
[22] E.E. Gilbert, Sulfonation and Related Reactions,
Wiley/Interscience, New York, 1965, pp. 62–92.
[23] Brandrup, Encyclopedia of Polymer Science and Engineering,
Wiley/Interscience, New York, 1985.
[24] L. James, A. Dicks, Fuel Cell Systems Explained, Wiley,
West Sussex, 2000.