Article

pubs.acs.org/JPCB

New Sulfonated Polystyrene and Styrene−Ethylene/Butylene−

Styrene Block Copolymers for Applications in Electrodialysis
Franciélli Müller,† Carlos A. Ferreira,*,† Lourdes Franco,‡,§ Jordi Puiggalí,‡,§ Carlos Alemán,*,‡,§
and Elaine Armelin*,‡,§
†
Departamento de Engenharia de Materiais, PPGEM, Universidade Federal do Rio Grande do Sul, Av. Bento Gonçalvez, 9500,
Setor 4, Prédio 74- 91501-970, Porto Alegre (RS), Brazil
‡
Departament d’Enginyeria Química, ETSEIB, Universitat Politècnica de Catalunya, Av. Diagonal 647, 08028, Barcelona, Spain
§
Centre for Research in Nano-Engineering, Universitat Politècnica de Catalunya, Campus Sud, Edifici C′, C/Pasqual i Vila s/n,
Barcelona E-08028, Spain
*
S Supporting Information

ABSTRACT: In this study we prepared blends of polystyrene (PS)

and high-impact polystyrene (HIPS) with poly(styrene−ethylene−
butylene) (SEBS) triblock copolymer. After sulfonation, blends were
used to fabricate ion-exchange membranes by solvent-casting and
subsequent thermal treatment to obtain homogeneous packing
densities. The morphology and structure of the blends were
investigated by scanning electron microscopy, atomic force micros-
copy, and FTIR spectroscopy. Furthermore, the thermal transitions
and stability of all the blends were characterized using calorimetric
techniques and compared with those of the individual polymers.
Analyses of the physical properties (i.e., ionic conductivity, ion-exchange capacity, water uptake, dimensional stability, mechanical
properties, etc.) showed that the performance of the PS-containing membranes is, in general, higher than that of the HIPS containing
one. Furthermore, the highest sulfonation degree was also found for the PS/SEBS membranes. The capabilities of the membranes
were tested by investigating the extraction of Na+ by electrodyalisis. Comparison of the percentage of extracted ions indicates that the
incorporation of SEBS results in a significant improvement with respect to membranes made of individual polymers.

■ INTRODUCTION
Membranes made of both natural and synthetic polymers have
been developed for over 50 years and currently comprise a wide
range of applications, such as water purification,1 gas separation,2
solvent dehydration,3 fuel cells,4,5 lithium batteries,6,7 biosensors
and biomaterials,8−11 and medical dialysis.12 In comparison with
traditional industrial separation processes, such as adsorption,
extraction, and distillation, membranes technology holds inherent
advantages (e.g., less reagent and solvent consumption, no chemical
additives, and recyclability), leading to reduced energy consump-
tion while the performance of separation processes increases.
A membrane is defined as an interface between two adjacent
phases acting like a selective barrier that regulates mass transfer
between two compartments. Among various kinds of mem-
branes, ion exchange membranes constitute the most useful
category. In particular, proton exchange membranes (PEMs) are
extensively used as electrolytes in electrochemical devices, such
as fuel cells, batteries, and electrolyzers, as well as barriers in
separation processes, such as filtration, gas separation, and
dialysis. PEMs are typically phasing segregated materials, where
a percolated network of a hydrophilic domain conducts protons
while the hydrophobic phase confers not only mechanical
strength but also dimensional and hydrolytic stability during
electrodialysis operation.
The performance of ion exchange membranes can be assessed
on the basis of the following aspects: flux and selectivity, cost of
production, thermal and chemical stabilities, and mechanical
strength.13 These properties are essentially related to the chemical
and physical nature of polymers. In the last few decades, the
design of materials able to combine high ionic conductivity and
durability, good mechanical strength, reduced permeability, and
low cost for high-volume production has become one the major
challenges in the field of new polymer materials for electrodialysis
applications.14−17
Sulfonated hydrocarbons are very promising ion exchange
membranes.18−23 Compared to Nafion, a commercially available
and widely studied fluorocarbon PEM manufactured by DuPont,
sulfonated hydrocarbon PEMs are generally easy to produce and
recyclable, relatively free from environmental pollution problems,
and can be synthesized using cheap monomers. Indeed, their
unique inconvenience is that, after a few months of use, they
need to be replaced due to porous obstruction.
Within this context, amorphous sulfonated polystyrene
copolymers (SPS), high-impact polystyrene (HIPS), and
Received: July 10, 2012
Revised: September 4, 2012
Published: September 19, 2012

© 2012 American Chemical Society 11767 dx.doi.org/10.1021/jp3068415 | J. Phys. Chem. B 2012, 116, 11767−11779
The Journal of Physical Chemistry B
poly(styrene−ethylene−butylene) triblock copolymer (SEBS)
are promising membrane materials, especially for dialysis applica-
tions. This is because of their high thermal and mechanical
stabilities and their relatively low production cost with respect to
that of Nafion. Furthermore, they maintain their mechanical
properties and have high water uptakes over a wide temperature
range.
In this study, we investigate and characterize SEBS-containing
blends that has been mixed with polystyrene (PS) and HIPS as
cation-exchange membranes (CEMs) for electrodialysis appli-
cations. Furthermore, a conducting polymer, polyaniline (PAni)
doped with camphorsulfonic acid (CSA), was added to enhance
both the conductivity and stability of these CEMs, the results
being compared with those obtained for other organic
membranes modified with conducting polymers.24−28 Figure 1
Figure 1. Chemical formula of the systems used in this work: (a)
polystyrene-b-(ethylene-co-butylene)-b-styrene triblock copolymer
(SEBS), (b) polystyrene homopolymer (PS), (c) high-impact
polystyrene (HIPS), (d) polyaniline doped with camphorsulfonic
acid (PAni-CSA), (e) Selemion AMV commercial membranes, and (f)
Selemion CMT.
depicts the chemical structure of SEBS triblock copolymer,
PS, HIPS graft copolymer, and PAni-CSA. In order to confer
ionic conductivity to the hydrophilic domain of the membrane,
the aryl groups of SEBS have been sulfonated using the
procedure described by Chlanda and Cooke.29 The properties of
these polymeric membranes are largely influenced by both the
phase morphology and the interfacial properties, which in turn
depend on the composition, the processing conditions, and the
compatibility between the components of the blend.30−34
Moreover, the impact of homogeneity on surface layers, which
is obtained through a thermal treatment after solvent-cast film
preparation, on the efficiency and resistance of the membranes
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has been also evaluated. Thus, the membranes reported in this
work have been found to exhibit a valuable combination of
mechanical, chemical, and electrochemical properties. The use
of PS and SEBS block copolymer is also expected to provide a
significant cost reduction compared to conventional technolo-
gies for the fabrication of commercial PEMs (e.g., Selemion).35
■ EXPERIMENTAL SECTION
Materials. PS (Mw= 27.5 × 103 g/mol) and HIPS (Mw =
16 × 103 g/mol) homopolymers, were kindly supplied by
Innova S.A. (PS-N2380 and HIPS-SR550). The SEBS, which
was purchased from Kraton Co. (catalog number G-1650M),
is a linear triblock copolymer with two PS end blocks (Mw=
10.3 × 103 g/mol) and a poly(ethylene-co-butylene) (PEB)
midblock (Mw = 53.3 × 103 g/mol). Solvents, metal salts,
and acid solutions employed were: 1,2-dichloroethane (Vetec,
ACS reagent, ≥99.0%), dimethylformamide (Vetec, ACS
reagent, ≥99.8%), methanol (Aldrich, anhydrous, 99.8%),
ethanol (Panreac, ACS reagent, ≥99.5%), acetone (Panreac,
NMR reagent, 99.8%), tetrahydrofuran (Panreac, PAI reagent,
99.5%), trichloromethane (Panreac, PAI reagent, 99.95%),
dimethyl sulfoxide (Panreac, PAI reagent, 99.95%), trifluoro-
acetic acid (Sigma, ReagentPlus, 99%), dichloroacetic acid
(Sigma, ReagentPlus, 99%), tetrachloromethane (Sigma,
anhydrous, ≥99.5%), o-xylene (Panreac, PS reagent 99%),
sodium chloride (Sigma, BioXstra, ≥99.5%), sulfuric acid
(Nuclear, ACS reagent, 95−98%), and acetic anhydride (Synth,
99.5%). Aniline (Nuclear, ACS reagent, 99.9%), ammonium
persulfate (Synth, reagent grade), hydrochloric acid (Sigma,
ACS reagent, 37%), and ammonium hydroxide (Synth, ACS
grade) were used for the synthesis of PAni emeraldine base,
which was performed using a standard method reported by
MacDiarmid and Epstein.36 The resulting polymer was doped
with CSA (Aldrich, purum, ≥98.%).
Blends and Membrane Preparation. Acid-bearing
polymers were prepared by sulfonation of the PS segments.
Sulfonation was carried out in 1,2-dichloroethane using the
procedure described in ref 29. PS (or HIPS) and SEBS blends,
in the ratio of 75% of homopolymer and 25% of triblock
copolymer, were prepared. In a 2 L three-necked flask equipped
with a dropping funnel, thermometer, and mechanical stirring,
60 g of PS (or 60 g of HIPS) was dissolved in 195 mL of
1,2-dichloroethane. In a 1 L Erlenmeyer flask equipped with a
magnetic stirring, 15 g of SEBS was stirred in 1,2-dichloro-
ethane until complete dissolution. After this, 19 mL of acetic
anhydride was added to the last solution, the mixture was
placed in the reaction flask containing PS (or HIPS), and the
contents were heated to 40 °C. Then, 6 mL of sulfuric acid was
added dropwise and the reaction was maintained at 40 °C, with
a controlled oil bath, for 5 h. Then, the reaction was cooled to
room temperature and the mixture was precipitated in a 50/250
(v/v) methanol/dimethylformamide solution. The precipitate
was washed with water until the residual water was pH 7, being
subsequently reduced in a rotary evaporator. The remaining
partially sulfonated PS/SEBS (or sulfonated HIPS/SEBS)
blend solution in dimethylformamide was poured on a glass
plate, spread to uniform thickness (100−150 μm) with a
spreader, and dried for 15 min at 110 °C in an oven.
Blends with low resistivity were prepared considering 5 wt %
of PAni doped with CSA (PAni-CSA) in the composition.
Aniline was polymerized according to the standard method
described in ref 36. Doped PAni was first filtered and then
treated with 1.0 M NH4OH to obtain the emeraldine base
dx.doi.org/10.1021/jp3068415 | J. Phys. Chem. B 2012, 116, 11767−11779
The Journal of Physical Chemistry B
form. Subsequently, PAni emeraldine base was doped with
1.5 M CSA and the solution stirred for 24 h.37 The conducting
polymer was added to the reaction after 5 h of sulfonation, and
the reaction remained under agitation for a further 30 min for
its complete dissolution. The blends modified with Pani-CSA
have been labeled as PS/SEBS/PAni and HIPS/SEBS/PAni.
The influence of the drying procedure on the membranes
properties has been evaluated for HIPS/SEBS blends
considering two different methods: (a) films dried at room
temperature by solvent casting and (b) films dried at 110 °C for
15 min in an oven and subsequently annealed overnight at
60 °C under vacuum. The membranes made of all the other
composition blends were prepared using procedure b.
Water Uptake Measurement and Ion-Exchange
Capacity (IEC). In order to evaluate the water absorption,
the “wet” and “dry” weights (Wwet and Wdry, respectively) were
obtained as follows. Membranes were equilibrated in deionized
water overnight at room temperature, blotted with a Kimwipe
to remove surface water, and finally weighted to obtain the
Wwet. Then, the membranes were kept in an oven at 80 °C for
12 h and weighted to obtain Wdry.38,39 The water uptake was
determined by the mass difference between the wet and the
dried membranes. The water absorption was calculated as the
percentage increase in mass over the dry weight:
Wwet − Wdry
water uptake = × 100%
Wdry (1)
To determine the ion-exchange capacity (IEC), the membranes
were equilibrated in 100 mL of 1 M HCl solution for 72 h. After
that, they were removed from the solution, and the excess of
acid was eliminated by washing the films repeatedly with distilled
water. Next, membranes were immersed in 1 M NaCl to
exchange protons by Na+, three renewed solutions being used in
this process. The amount of H+ in such three solutions was
determined by titration with 0.005 M NaOH to a phenolph-
thalein end point. The IEC was expressed in milliequivalents of
H+ per gram (mequiv·g−1) of the dry weight of the membrane:40
VNaOHMNaOH
IEC =
Wdry (2)
where VNaOH and MNaOH are the blank-corrected volume (mL)
and molar concentration (mol/L) of NaOH solution, respectively.
Both the IEC and the water uptake values were taken as the
average values of five membrane samples.
Electrodialysis. Tests were conducted using a three-
compartment cell described in our previous works.25,41
Platinized titanium electrodes were used as anode and cathode.
The volume in each compartment was 200 mL. Membranes
were immersed in the working solutions for 48 h to reach an
equilibrium state. A pseudostationary state was achieved with
pre-electrodialysis for 15 min. After this period, solutions were
replaced by new ones, and the experiment was restarted.
Solutions of NaCl (0.1 M) were prepared with deionized water
and poured on the working compartment cell located on the
middle. In the compartments located on the right and on the
left of the working compartment cell, solutions of Na2SO4 0.1 M
were poured. The anionic membrane was the commercial
Selemion AMV, which was purchased from Asahi Glass Co.
(Figure 1e), and the cationic membranes were those prepared
in this study. The effective area of the membranes was 10 cm2.
Tests were conducted by applying a current density of 3.5 mA/cm2
for 4 h at 20 ± 2 °C.
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The limiting current density (ilim) was derived from the
variation of the membrane potential (φm) against the applied
current density (i).42 The i−φm polarization curves were
performed with all the membrane systems described above. The
value of i was increased every 2 min, and the corresponding φm
was determined using two platinum contact electrodes adhered
to the surface of the membrane. Flame photometric determina-
tions with a Digimed DM-61 flame photometer were used to
obtain the concentration of Na+.
Instrumentation and Techniques. The sulfonation
degree (SD%) of the membranes was determined by the
Standard Test Method ASTM International D5453,43 the results
being corroborated by 1H NMR (in DMSO-d6 or CDCl3) using
a 300 MHz Bruker AMX300 spectrometer operating at
300.1 MHz. Intrinsic viscosities were measured from polymer
solutions in toluene or dimethylformamide, using an Ubbelohde
viscometer thermostated at 25.0 ± 0.1 °C. Structural character-
ization of membranes was performed using a Thermo Scientific
Nicolet 6700 FTIR spectrophotometer. Samples were placed
in an attenuated total reflection (ATR) accessory (Thermo
Scientific Smart Orbit) with a diamond crystal. The FTIR
spectra were obtained after 32 scans at a resolution of 4 cm−1,
in a spectral range of 400−4000 cm−1, in transmittance mode.
Scanning electron microscopy (SEM) studies were carried out
using a focused ion beam Zeiss Neon 40 microscope equipped
with an energy dispersive X-ray (EDX) spectroscopy system and
operating at 30 kV. Samples were mounted on a double-sided
adhesive carbon disk and sputter-coated with a thin layer of carbon
graphite to prevent sample charging problems. Topographic AFM
images were obtained with a Molecular Imaging PicoSPM using a
NanoScope IV controller under ambient conditions. The root-
mean-square (rms) roughness (r) was determined using the
statistical application of the Nanoscope software, which
calculates the average considering all the values recorded in
the topographic image with the exception of the maximum and
the minimum. AFM measurements were performed on various
parts of the films, which produced reproducible images similar
to those displayed in this work.
Differential scanning calorimetry (DSC) was performed on a
TA Instruments Q100 differential scanning calorimeter using
a heating rate of 100 °C/min under nitrogen gas. Data were
collected from −90 to 200 °C. Due to the amorphous behavior
of polymers employed in this work, melting peaks are not
expected, and the Tg values were determined from the second
heating run after quenching the sample from the melt state.
Thermogravimetric analysis (TGA) of the membranes was per-
formed using a Q50 thermogravimetric analyzer (TA Instru-
ments) at a heating rate of 20 °C/min under a nitrogen
atmosphere. Prior to DSC and TGA measurements, all samples
were dried under vacuum at 60 °C overnight.
Ionic conductivity was measured by ac impedance spectros-
copy with an AutoLab PGSTAT302N frequency response
analyzer (FRA) employing a two-electrode configuration and
a procedure described elsewhere.44,45 A 10 mV sinusoidal ac
voltage over a frequency range from 10 kHz to 10 mHz was
applied. Conductivity values reported in this work correspond
to the average of five membrane samples.
Mechanical properties were evaluated using a universal
testing machine (Zwick GmbH & Co., model Z2.5/TN1S)
with integrated testing software (testXpert, Zwick). Samples
used for the test stress−strain assays consist of rectangular
specimens with dimensions 30 mm long × 4 mm wide. The
initial grip separation was set at 10 mm, and the cross-head
dx.doi.org/10.1021/jp3068415 | J. Phys. Chem. B 2012, 116, 11767−11779
The Journal of Physical Chemistry B
speed was 0.80 mm/min. Mechanical properties of the
membranes were determined from stress−strain curves derived
from uniaxial tensile tests. Specifically, these properties were the
Young’s modulus (E), the elongation or strain at break (σmax),
the yield strength or stress at maximum force (εσ max), and the
tensile strength or stress at break (εb). All the mechanical assays
were conducted at room temperature. The mechanical parameters
reported in this work were averaged over 10 independent
measurements for each dry and wet membrane. The dry
membranes correspond to polymer films with a post-thermal
annealing, whereas the wet membranes refer to dry membranes
after their immersion in deionized water at room temperature
for 24 h.
■ RESULTS AND DISCUSSION
Sulfonation Degree, IEC, Water Uptake, Conductivity,
and Solubility Parameters. Membrane sulfonation was
carried out by reacting acetic anhydride and sulfuric acid with
a mixture of PS or HIPS and SEBS. Thus, the reaction of acetic
anhydride with sulfuric acid produces acetylsulfuric acid, which
in turn reacts with the aryl groups to produce the sulfonated
membrane.29 The reaction time is a crucial factor since,
although the number of sulfonic acids in the styrene aromatic
ring increases with the reaction time, the chemical stability and
life performance of the membranes used in electrodialysis
decrease with increasing reaction time. In this work the sulfona-
tion reaction time was 5 h in all cases, which was reported to be
suitable for the lifetime of the membrane performance.
The resulting partially sulfonated binary blends were soluble
in common polar aprotic solvents (e.g., chloroform, tetrahy-
drofurane, dimethyl sulfoxide, and dimethylformamide) and
completely insoluble in apolar solvents. PAni-CSA-containing
blends were partially soluble in all the solvents mentioned
for binary blends with the exception of chloroform. Solubility
was also highly dependent on the number of sulfonic groups
incorporated to the polymer matrix. Due to the chemical
structure of the blends, the solvent-cast films exhibited relatively
good dimensional stability. They were tough and flexible,
being excellent candidates for the fabrication of electrodialysis
membranes.
Table 1 summarizes the main properties of the polymer
membranes prepared in this study. HIPS/SEBS presents low
intrinsic viscosity in toluene solution, while PS/SEBS showed
the highest intrinsic viscosity determined by capillary viscosimetry
Table 1. Chemical Composition, Intrinsic Viscosity,
Sulfonation Degree (SD), Water Uptake, Ion-Exchange
Membrane (IEC), and Conductivity Parameters Measured
for the Blends Made of PS or HIPS and SEBS, with and
without Conducting Polymer
intrinsic water
viscositya SDb uptake IECc conductivityd
sample (dL/g) (%) (wt %) (mequiv·g‑1) (S/cm)
HIPS/SEBS 0.02* 11 13 0.36 1.6 × 10−9
HIPS/SEBS/ 0.08* 9 8 0.51 7.1 × 10−9
PAni
PS/SEBS 1.43# 13 18 0.86 6.3 × 10−9
PS/SEBS/PAni 1.32# 11 14 1.24 1.5 × 10−7
a
Measured by capillary viscosimetry in *toluene and #dimethylforma-
mide at 30 °C. The intrinsic viscosity of PS, HIPS, and SEBS measured
in toluene is 0.23, 0.16, and 0.15 dL/g. bMeasured according to the
procedure indicated in the ASTM D5453-09.43 cMeasured by titration.
d
Measured by ac impedance in the solid state and at room temperature.
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in dimethylformamide (i.e., this blend was insoluble in toluene).
The reduced and inherent viscosities (ηred and ηinh, respectively)
of PS/SEBS blends increase progressively with decreasing
concentration. This unusual behavior has been attributed to the
ionic strength promoted by the mobile ions located inside the
polymer matrix, due to the presence of the counterions of
the sulfonate groups. PS/SEBS blends exhibited the highest
sulfonation degree, having better polyelectrolyte properties than
HIPS/SEBS copolymers. Thus, polyelectrolytes expand in polar
solvents like dimethyl sulfoxide, dimethylformamide, or water
solutions. The viscosity values showed in Table 1 for PS/SEBS
copolymers in dimethylformamide solution were calculated using
the Fuoss and Strauss equation46 and cannot be taken by simple
extrapolation of ηsp/c to zero concentration.
Water sorption increased with concentration of sulfonate
groups due to the strong hydrophilicity of this functionality,
as described in other works.47,48 The water uptake and the
number of water molecules coordinated by the −SO3− group of
the sulfonated HIPS/SEBS blends were reduced after the heat
treatment. This result is associated with both an increase of the
packing density and a reduction of the free volume for the
transport of proton and water molecules, as will be discussed in
detail in the next subsection.
The dimensional stability of the membranes increases as the
blend affinity for water decreases. Accordingly, as the blend
affinity for water increases, ionic transport resistance decreases.
Water absorption is slightly higher for the membranes prepared
with PS (e.g., 18% and 14% for PS/SEBS and PS/SEBS/PAni,
respectively) than for those obtained using HIPS (e.g., 13% and
8% for HIPS/SEBS and HIPS/SEBS/PAni, respectively). The
latter values refer to membranes dried in an oven, even although
membranes dried at room temperature displayed higher water
uptakes (not included in Table 1). This must be attributed to
the fact that the latter present a more porous morphology than
the former, as observed by SEM. In particular, the highest water
absorption was obtained for the HIPS/SEBS membrane dried at
room temperature (36%).
The IEC measured for different membranes are included in
Table 1. The IEC is higher for the PS-containing membranes
than for those made of HIPS. Indeed, the IEC of the HIPS/
SEBS membrane is higher before annealing (0.42) than after
annealing (0.36), evidencing the influence of the drying
process. The IECs found for the PAni-containing membranes
is higher than that found for membranes without conducting
polymer. This has been attributed to both the hydrophilicity of
PAni-CSA, which facilitates the ions’ transport, and the higher
ionic conductivity achieved for conducting polymer-containing
membranes. Thus, PS/SEBS/Pani shows the highest ionic con-
ductivity (Table 1) and IEC. Similarly, the values of these two
properties are higher for HIPS/SEBS/PAni than for HIPS/SEBS.
The sulfonation degree (SD), which depends on the reaction
time, was quantified by UV fluorescence and confirmed by NMR
spectroscopy. As in this study, the reaction time was maintained
as a constant, so slight differences in the SD should be essentially
attributed to the polymer matrix composition. Moreover, the SD,
which ranged from 9.3% to 13.1%, was smaller than that
reported for commercial and noncommercial membranes.49,50
1
H NMR analysis (see Supporting Information) confirms the
low sulfonation degree of polymer blends. The main peaks,
attributed to the aromatic rings from polystyrene units, appear
at 6.4−7.2 ppm. NMR spectra of PS/SEBS and PS/SEBS/PAni
partially sulfonated graft polymers exhibit a broad peak at
7.4 ppm corresponding to the C−H aromatic protons adjacent
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The Journal of Physical Chemistry B
Figure 2. FTIR-ATR spectra of (a) PS and SEBS individual polymers and the sulfonated PS/SEBS blend and (b) HIPS and SEBS individual
polymers and the sulfonated HIPS/SEBS blend. Asterisks indicate C−H out-of-plane bending vibrations.
to the sulfonic groups and one additional peak at 8.1 ppm
corresponding to the OH dynamic group. However, HIPS/
SEBS blends show a modest shoulder of C−H aromatic peak
close to 7.2 ppm, indicating a very low ratio of C−H adjacent
sulfonic groups compared to PS/SEBS copolymers. We
conclude that HIPS graft polymer needs higher reaction time
with acetic anhydride and sulfuric acid for effective sulfonation
degree in polymer chains. Quantification of SD from C−H
aromatic peaks was not possible due to the overlapping of
aromatic signals of nonsulfonated rings.51−53
Structural and Thermal Characterization. FTIR spec-
troscopy was used to corroborate the sulfonation of the blends.
The FTIR-ATR spectra of the individual components (PS,
SEBS, and HIPS) are compared with those of the sulfonated
PS/SEBS and HIPS/SEBS in Figure 2. The mean peaks of PS
(Figure 2a) are observed at 3079, 3058, and 3025 cm−1 (C−H
aromatic stretching, triple bands); 2917, 2848 cm−1 (C−H
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aliphatic stretching); 1600, 1490, and 1450 cm−1 (CC
aromatic stretching); and 1027 and 904 cm−1 (C−H in-plane
bending); the strong absorption bands at 748, 694, and
538 cm−1 are attributed to C−H out-of-plane bending. The
bands of the SEBS copolymer (Figure 2a) are detected at 3060,
3025, 2918, 2850, 1602, 1493, 1456, 1375, 756, 698, 543 cm−1;
comparison with PS evidences a significant enhancement of the
bands associated with the C−H aliphatic groups at ∼3000
cm−1. The sulfonation reaction produces two new intense peaks
in the PS/SEBS blends at 1215 and 1161 cm−1 (Figure 2a),
which correspond to the asymmetric and symmetric SO
stretching vibrations, respectively, indicating the success of the
sulfonation reaction.54 Another strong absorbance, which has
been attributed to the C−S stretching, is detected at 1124 cm−1.
The appearance of characteristic peaks associated with the
symmetric stretching of the −SO3− group and the in-plane
bending of the para-substituted phenyl ring at 1030 and 1004 cm−1,
dx.doi.org/10.1021/jp3068415 | J. Phys. Chem. B 2012, 116, 11767−11779
The Journal of Physical Chemistry B Article

Figure 3. DSC curves of sulfonated PS/SEBS and HIPS/SEBS blends compared to nonsulfonated PS, SEBS, and HIPS. All curves are referred to the
second heating run with the membranes previously annealed overnight at 60 °C and under vacuum.

Table 2. Thermal Properties of Sulfonated Blends and Nonsulfonated Individual Polymers (PS, HIPS, and SEBS)
sample Tg1a (°C) Tgβa (°C) Tgαa (°C) Tma (°C) ΔH (J/g) Td,5%b (°C) Td,50%b (°C) Tonsetb (°C) char yieldc (%)
PS 104 − − − − 388 426 428 0.04
k 95 − − − − 393 437 437 1.10
SEBS − −57 93 17 20.5 406 450 454 0.16
PS/SEBS 127 −60 95 17 0.72 303 403 411 3.24
PS/SEBS/PAni 130 −63 95 17 0.68 281 403 410 5.46
HIPS/SEBS 104 −61 97 16 0.79 247 436 446 4.43
HIPS/SEBS/PAni 104 −56 96 18 0.58 246 434 439 10.7
a
Glass transition (Tg) and melting (Tm) temperatures were obtained by DSC. bDecomposition temperatures were obtained by TGA for 5% and 50%
of weight loss. Tonset is the temperature at which the sample shows a significant mass loss. cAt 600 °C and under nitrogen gas flow.

respectively, confirm the sulfonation of the PS/SEBS blend.
Furthermore, the broad and weak absorption band between
3600 and 3300 cm−1 in the sulfonated membrane indicates
the presence of a significant number of −OH from the −SO3H
groups, corroborating that the polymer blend was successfully
sulfonated. Comparison of the HIPS, SEBS, and HIPS/SEBS
FTIR spectra (Figure 2b) allowed us to conclude that, as
expected, the latter blend was also successfully sulfonated. Thus,
the main absorption bands from −SO3H groups detected in the
spectrum of the blend, and not identified in those of individual
HIPS and SEBS, were used as the reference.
On the other hand, we should mention that FTIR spectro-
scopy was not useful for distinguishing the presence of PAni in
the polymeric matrix, due to the very low intensity of CC or
CN groups. In spite of this, we detected the presence of PAni
in PS/SEBS/PAni and HIPS/SEBS/PAni by Raman spectros-
copy (not shown). The PAni-CSA Raman spectrum was similar
to those described in the literature.55,56 Peaks at 1168 and
1339 cm−1 are related to C−H bonds of quinoid rings and the
formation of the polaronic C−N+ group typically found in
doped PAni, respectively. The peaks associated with the CN
and CC stretching appeared at 1506 and 1580 cm−1,
respectively, while the SO groups of CSA were identified by
a broad band at 1034−1000 cm−1. In the PS/SEBS/PAni and
HIPS/SEBS/PAni membranes spectra peaks of PAni were
observed, demonstrating the incorporation of the conducting
polymer into the blend. Moreover, the incorporation of PAni
was also visually corroborated because of the change to a dark
color (i.e., the addition of conducting polymers provokes a
11772
change of color, even when a very small concentration is used,
because of the electrochromic properties of these materials).
Most sulfonated hydrocarbon CEMs are derived from
amorphous glassy polymers in the nonequilibrium state.
Amorphous glassy polymers generally encompass a free volume
that is higher than the minimal free volume, which is obtained
from the difference in specific volume when the transition from
the liquid to the hypothetical equilibrium glassy state occurs.
Thus, the thermal history of glassy polymers can significantly
influence the packing density of their polymer chains. All the
membranes synthesized in this study were previously annealed
overnight at 60 °C under vacuum before DSC and TGA
analysis, unless other conditions are explicitly stated.
No endothermic peak from a fusion process was detected in
the DSC curves of the blends, which has been related with a
material completely amorphous and a pronounced Tg response,
with the exception of SEBS. The latter copolymer exhibits three
transitions that have been assigned to α relaxation of the PS
segment (Tgα = 93 °C), the β relaxation (Tgβ = −57 °C), and
melting temperature (Tm ∼ 17 °C) of the elastomeric block,
the latter corresponding to the maximum endotherm peak just
after the first Tg. The small area of the melting endotherm
(ΔH = 20.5 J/g) indicates that there is a very small percentage
of crystallinity in the material (Figure 3).57 The addition of PS,
which shows only one glass transition close to 104 °C, to SEBS
results in a blend with glass transition temperature (Tg1 = 127 °C)
higher than those of the two individual components.
Incorporation of PAni-CSA 5 wt % to PS/SEBS does not affect
significantly the thermal properties of the blend, as is reflected in
Table 2. On the other hand, the two sulfonated blends retain
dx.doi.org/10.1021/jp3068415 | J. Phys. Chem. B 2012, 116, 11767−11779
The Journal of Physical Chemistry B
Figure 4. Thermogravimetric analysis of membranes prepared by solvent casting: (a) PS, SEBS, and HIPS (nonsulfonated) and (b) PS/SEBS, PS/
SEBS/PAni, HIPS/SEBS, and HIPS/SEBS/PAni blends (sulfonated). All samples were previously annealed overnight at 60 °C under vacuum with
the exception of that explicitly indicated.
signs of α and β relaxations from SEBS copolymer, which should
be attributed to phase separation. The Tg1 transition of the
blends varies with the composition, whereas Tm is a modest
shoulder with no practical significance. Substitution of PS by
HIPS in the blend to extend the chains and incorporate the
rubbery segment provokes a higher mobility of the chains. This
produces a slight increase in the Tg1 with respect to that of the
HIPS homopolymer (Figure 3).
TGA of PS, HIPS, and SEBS, which are displayed in Figure 4a,
exhibit one degradation step only. The highest decomposition
temperature (Tonset) was obtained for SEBS (Table 2).
However, blends present three well-defined degradation
steps, as shown in Figure 4b. According to the literature,48,52
the first step (between 50 to 200 °C) has been related to the
loss of residual water that was retained in the samples because
of the interactions with the sulfonic groups. The second weight
loss, which occurs at around 250−340 °C, has been attributed
to the elimination of sulfonic acid groups. Finally, the third
step, which depends on the blend composition, corresponds to
11773
Article
the polymer chain degradation. Comparison of the thermog-
ravimetric curves of sulfonated HIPS/SEBS samples dried at
room temperature or under vacuum reveals that membranes
submitted to the latter drying process suffered a partial elim-
ination of sulfonic acid. Thus, the weight loss observed at
around 250−340 °C is lower for samples dried under vacuum
than for those dried at room temperature. Shi and Holdcroft52
reported not only that highly sulfonated membranes increase
the loss weight in the 50−200 °C region but also that the
degradation steps of these samples are sharper than those with
low degree of sulfonation. These features corroborate our
hypothesis about the formation of strong intermolecular
interaction between sulfonic acid groups and water molecules.
On the other hand, the presence of a low concentration
(5 wt %) of PAni-CSA does not influence the thermal stability
of the blends, even though the residual char at 600 °C is higher
than for blends without conducting polymer (i.e., 5.5% and
10.7% for PS/SEBS/PAni and HIPS/SEBS/PAni, respectively).
Degradation temperatures are listed in Table 2.
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The Journal of Physical Chemistry B Article

Figure 5. Stress−strain curves of sulfonated membranes annealed at 60 °C under vacuum overnight (dry) and exposed to a high humidity chamber
(RH 100%, wet): (a) PS/SEBS, (b) PS/SEBS/PAni, (c) HIPS/SEBS, and (d) HIPS/SEBS/PAni blends.

Table 3. Mechanical Properties Obtained for Polymer Blends

E (MPa) σmax (MPa) εσ max (%)
polymer film dry wet dry wet dry wet
PS/SEBS 1046 ± 4 779 ± 6 28 ± 2 19 ± 0.6 4.4 ± 0.4 8.1 ± 2
PS/SEBS/PAni 685 ± 7 592 ± 8 19 ± 0.3 12 ± 0.8 4.7 ± 0.6 3.8 ± 0.3
HIPS/SEBS 811 ± 7 545 ± 6 21 ± 0.3 17 ± 0.5 12.3 ± 1.3 11.6 ± 1.1
HIPS/SEBS/PAni 280 ± 4 235 ± 3 7 ± 0.3 4 ± 0.05 6.4 ± 0.6 4.4 ± 0.2

Mechanical Properties. The stress−strain curves of PS/
SEBS, PS/SEBS/PAni, HIPS/SEBS, and HIPS/SEBS/PAni
blends are displayed in Figure 5, while the Young’s modulus,
tensile strength, and elongation at break are listed in Table 3. In
order to avoid the negative influence of the packing density
associated with the free-volume inside glassy polymer chains,
samples were submitted to thermal annealing before stress−strain
studies. Thus, the annealing process is supposed to stabilize the
glassy polymers, inducing densification of the polymer matrix.
This restricts the polymer chain mobility, and the membrane
plasticization effects induced by the absorbed small molecules
(e.g., water or solvents) are minimized.58 Mechanical assays
indicate that all blends undergo yielding at roughly the same
stress level and present brittle−ductile behavior. Thus, the
elongation of the samples is not accompanied by any significant
reduction in the cross-sectional dimensions (macroscopic
necking) up to fracture. The flow stress follows the same
trend, with the exception of the wet sulfonated PS/SEBS blend,
which showed a slight neck section with 5−8% of elongation
(Figure 5a). The highest and the lowest tensile strengths were
11774
obtained for the dry sulfonated PS/SEBS (28 ± 2 MPa) and the
dry sulfonated HIPS/SEBS/Pani (7 ± 0.3 MPa). As expected,
the incorporation of PAni-CSA produced deterioration of the
mechanical properties, even in the wet samples (Table 3 and
Figure 5b,d). This effect was previously described for other
related systems.59,60
Regarding to the Young’s modulus, PS-containing blends
showed the highest modulus (1046 and 779 for dry and wet,
respectively). The presence of rubber phases in HIPS increases
the deformation and reduces the flow resistance of the PS matrix.
Thus, the elastomer supports part of the load in the stage prior
to rupture, which is displayed for both dry and wet HIPS/SEBS
membranes (Figure 5c).
The Young’s modulus was lower for the wet membranes
than for the dry ones in all cases, indicating that the rigidity
decreases when the membrane hydration increases. Hydration
affects the membranes in the following way: (1) membranes
swell as the ionic regions grow with the incorporation of water
and (2) molecular fragments with charged end groups become
more mobile.61 However, these effects were relatively low in the
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The Journal of Physical Chemistry B Article

systems studied in this work because of the applied thermal

annealing treatment. Thus, hydration only caused a slight reduc-
tion of Young’s modulus and tensile strength with respect to the
values determined for dry films. PS/SEBS is an exception to this
behavior, its higher hydration being attributed to the lower
densification of the polymeric matrix compared to HIPS/SEBS.
SEM and AFM Studies. In addition to the chemical
structure, composition, and thermal properties, preparation
conditions are of fundamental importance in CEMs design. The
thermal annealing applied on sulfonated hydrocarbon polymers
has been found to alter the macroscopic characteristics of
CEMs studied in this work. The homogeneity and porosity
of membranes prepared with partially sulfonated blends and
PAni-CSA have been investigated with SEM, the resulting
morphologies of films prepared by solvent casting and after
annealing treatment being compared.
Figure 6 displays SEM micrographs for PS, HIPS, and SEBS
as reference. Low-magnification images show smooth and
regular surfaces. However, before annealing, PS presents a
typical matrix droplet structure at the surface with high free-
volume density and some porosity, as is reflected in the high-
magnification micrograph (Figure 6a, inset). HIPS presents
the most homogeneous surface with nondroplet structure
(Figure 6b), whereas a phase separation between the PS and
the −EB− block has been found in SEBS. This separation is
evidenced by the appearance of white zones randomly distributed
on the film surface (Figure 6c).
Prior to annealing, the PS/SEBS blend does not present well
distributed phases, indicating immiscibility between the triblock
copolymer and the homopolymer. The −EB− block separation
phase is clearly identified in the micrometric (Figure 7a) and
nanometric images displayed in Figure 7b, respectively. On the
other hand, the miscibility of SEBS with HIPS is better than
with PS, even before annealing. Thus, HIPS/SEBS micrographs
(Figure 8a,b) show a free-volume surface density with bigger
and coarser droplet structure than PS (Figure 6a,b) but without
white regions like those identified in PS/SEBS films.
After annealing, polymer blends present higher homogeneity
and nondroplet structures, corroborating that thermal treatment
significantly improves the packing density of thermoplastic
blends (Figures 7c and 8c). On the other hand, sulfonated
PS/SEBS/PAni membranes show a homogeneous and compact
structure (Figure 7d), whereas incorporation of PAni to
HIPS/SEBS results in an immiscible system as is evidenced
by the appearance of numerous particles at the film surface
(Figure 8d). Figure 6. SEM micrographs of the individual polymers used as
Differences in the membrane surface morphology can be reference: (a) PS, (b) HIPS, and (c) SEBS. The inset in part a denotes
expressed in terms of roughness. AFM was used to measure the a high-magnification image showing the porosity inside the PS film
prepared by solvent-casting and without annealing treatment (scale
average roughness (r) of all membranes investigated in this bar: 2 μm).
work, surface topography images being displayed in Figure 9.
The roughness values determined for PS/SEBS and PS/SEBS/
PAni membranes are very similar (r = 17 and 15 nm, res- AFM measures on membranes exhibiting droplet structures (i.e.,
pectively), proving that PAni-CSA is well-dispersed in the prior to the annealing treatment) were difficult due to the large
polymer matrix, which is fully consistent with the SEM size of height profile.
micrographs. Substitution of PS by HIPS in the binary blend Electrodialysis Study for Na+ Extraction. Limiting
composition promotes a higher roughness (r = 55.0 nm) due to current density (ilim) values were determined for the polar-
the volume density of the grafted polymer. In contrast, the ization curves (i.e., variation of the membrane potential, ϕm,
roughness of the HIPS/SEBS/PAni membrane (r = 19.6 nm) against the applied current density, i) using the Cowan−Brown
was significantly lower than that of HIPS/SEBS. This is probably procedure.62,63 At low i values, the linear relation with ϕm
because the regions analyzed by AFM do not represent the indicates the quasi-equilibrium state in the interface between
ternary blend topography (i.e., the particles observed by SEM the membrane and the solution. Such linear behavior is lost to
were presumably PAni clusters not detected by the AFM tip, and reach a plateau region, which allows us to identify the ilim value
polymer surface is deformed). Finally, we should mention that at the inflection point of the curve. The ilim values of PS/SEBS,
11775 dx.doi.org/10.1021/jp3068415 | J. Phys. Chem. B 2012, 116, 11767−11779
The Journal of Physical Chemistry B Article

Figure 7. SEM micrographs of PS/SEBS blends: (a) low magnification (before annealing), (b) high magnification (before annealing), (c) low
magnification (after annealing); and (d) PS/SEBS/PAni (after annealing).

Figure 8. SEM micrographs of HIPS/SEBS blends: (a) low magnification (before annealing), (b) high magnification (before annealing), (c) low
magnification (after annealing), and (d) HIPS/SEBS/PAni (after annealing).

11776 dx.doi.org/10.1021/jp3068415 | J. Phys. Chem. B 2012, 116, 11767−11779

The Journal of Physical Chemistry B
Figure 9. AFM topographic image of the membrane surfaces: (a) PS/SEBS, (b) PS/SEBS/PAni, (c) HIPS/SEBS, and (d) HIPS/SEBS/PAni. Left:
front image. Right: 3D image.
HIPS/SEBS, PS/SEBS/PAni, and HIP/SEBS/PAni mem-
branes ranged from 3.9 to 5.1 mA·cm−2. Electrodialysis assays
were carried out using ilim = 3.5 mA·cm−2, which is relatively
close to the values derived from the polarization curves, and
membranes with an effective area of 10 cm2 in all cases.
Table 4 shows the percentage of Na+ extracted through the
membranes fabricated in this work. For comparison, Na+
extraction results recently obtained for HIPS/PAni membranes
using the same experimental conditions (i.e., PAni doped with
CSA, ilim = 3.5 mA·cm−2 and area of the membrane = 10 cm2)
have been included in Table 4.28 Furthermore, electrodialysis
control measurements have been also performed using
11777
Article
Selemion CMT (Figure 1f), which is currently considered
among the most advanced commercial membranes. For the
membranes prepared in this work, the largest transport of Na+
was found for the PS/SEBS (24.8%), the percent extraction
obtained for HIPS/SEBS being ∼5% smaller. This should be
attributed to the fact that, even after annealing, the partial
immiscibility between the triblock copolymer and the
homopolymer favors the formation of a porous interface region
in the former. The addition of PAni-CSA to PS/SEBS and
HIPS/SEBS membranes does not have any positive effect in the
extraction. Indeed, the percentage of Na+ extracted decreases
by only 1.3% and 0.2%, respectively.
dx.doi.org/10.1021/jp3068415 | J. Phys. Chem. B 2012, 116, 11767−11779
The Journal of Physical Chemistry B
Table 4. Percent Extraction (E%) and Extraction in mg/L
(Emg/L) of Na+ for Membranes Prepared in This Work and
Commercial Selemion CMT (control)b,a
membrane E% Emg/L
d
PS/SEBS 24.8 519
PS/SEBS/PAnid 23.5 510
HIPS/SEBS (before annealing)d 21.0 435
HIPS/SEBS (after annealing)d 20.1 412
HIPS/SEBS/PAnid 19.9 411
HIPS/PAni (solvent dissolution)c,e 0.3 5 fabricated in this study ranges from 24.8% to 19.9%, which
HIPS/PAni (mechanical mixture)c,e 10.3 90
Selemion CMT 63.4 1242
a
Data previously reported for HIPS/PAni have been included for
comparison.c. bilim = 5 mA·cm−2 and area of the membrane = 10 cm2
in all cases. cFrom ref 28. dElectrodialysis assays performed using a
three-compartment cell. eElectrodialysis assays performed using a five-
compartment cell.
Table 4 clearly shows that SEBS improves significantly the
transport of Na+ found in our previous study for HIPS/PAni
membranes, which ranged from 0.3% to 10.0% depending on
the experimental procedure used for their fabrication.28 This
should be attributed to the fact that the impact resistance of
the HIPS/SEBS blend is smaller than that of HIPS, allowing
increasing the permeability of ions transport in the former. On
the other hand, inspection of the results obtained using the
Selemion CMT indicates that, although the blends prepared in
this work represent an important advance in the field, more
work is still needed to reach the performance of the commercial
membranes. Thus, the membranes fabricated in this work are
still ∼2.5 times less effective than the commercial Selemion
CMT. This difference has been attributed to the fact that the
latter presents a significantly higher concentration of sulfonic
groups than the SEBS-containing membranes. Accordingly, our
future research in this field will be essentially oriented toward
the search of effective methods to increase the concentration
of sulfonic groups in HIPS/SEBS and, especially, PS/SEBS
membranes.
■
CONCLUSIONS
Sulfonated PS/SEBS, HIPS/SEBS, PS/SEBS/PAni, and HIPS/
SEBS/PAni membranes have been fabricated and characterized.
The sulfonation degree, which ranged from 9.3% to 13.1%, was
of fundamental importance for the dimensional stability and
water uptake. Thus, the dimensional stability and affinity for
water decreases and increases, respectively, with increasing
sulfonation degree. However, the ion-exchange capacity was
also influenced by the ionic conductivity of the membranes,
which was increased by the addition of PAni-CSA. Thus, the
membrane with the highest ionic conductivity, PS/SEBS/PAni,
was found to present the highest ion-exchange capacity.
The chemical structural, thermal, and mechanical properties
of the blends have been characterized using FTIR spectroscopy,
calorimetric studies, and stress−strain assays, respectively.
PS-containing membranes present higher tensile strength and
Young modulus than the HIPS-containing one. The annealing
treatment has been found to induce densification of the polymer
matrix, producing a reduction in the mobility of the molecules.
SEM micrographs show that the miscibility of SEBS is better
with HIPS than with PS, phase separation being observed
in PS/SEBS copolymers. However, homogeneity improves after
annealing, evidencing the influence of the thermal treatment in
11778
Article
the packing density. On the other hand, PAni-CSA has been
found to be completely immiscible with HIPS/SEBS, while it
forms homogeneous and compact mixtures when mixed with
PS/SEBS.
Electrodialysis assays showed that transport of Na+ decreases
as follows: PS/SEBS > PS/SEBS/PAni > HIPS/SEBS > HIPS/
SEBS/PAni. Thus, the Na+ extraction ability is higher for the
PS-containing membranes than for the HIPS-containing ones,
incorporation of PAni-CSA having a negative effect in both cases.
Moreover, the percentage of Na+ extracted using the membranes
represents a very noticeable improvement with respect to HIPS/
PAni membranes previously studied.28 Thus, SEBS modulates
the impact resistance of HIPS facilitating the ion transport and,
therefore, this triblock copolymer should be considered as a very
effective material for the fabrication of CEMs.
■
ASSOCIATED CONTENT
*
S Supporting Information
1
H NMR spectra of PS, SEBS, HIPS, PS/SEBS, and PS/HIPS.
This material is available free of charge via the Internet at
http://pubs.acs.org.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: ferreira.carlos@ufrgs.br (C.A.F.), carlos.aleman@upc.
edu (C.A.), and elaine.armelin@upc.edu (E.A.).
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work has been supported by CAPES-MICINN International
Cooperation Program from Brazilian and Spanish Education and
Science Ministries (PHB2007-0038-PC), MICINN and FEDER
funds (MAT2009-09138 and MAT2009-11513) and by the
DIUE of the Generalitat de Catalunya (2009SGR925,
2009SGR1208). We are indebted to Mr. D. Aradilla for his
assistance in AFM analyses. F.M. acknowledges financial support
from the CAPES agency (grant no. BEX 4463/10-2) for her one
year stay at UPC. Support for the research of C.A. was received
through the prize ‘‘ICREA Academia’’ for excellence in research
(funded by the Generalitat de Catalunya).
■
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