Chemical Engineering Journal 390 (2020) 124612

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Chemical Engineering Journal

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Preparation and characterization of a new composite conductive T

polyethersulfone membrane using polyaniline (PANI) and reduced graphene
oxide (rGO)
⁎
Eduardo L. Subtila, , Jamile Gonçalvesa, Hugo G. Lemosa, Everaldo C. Venancioa,
José Carlos Mierzwab, Juliana dos Santos de Souzac, Wendel Alvesc, Pierre Le-Clechd
a
Engineering, Modeling and Applied Social Sciences Center (CECS), Federal University of ABC (UFABC), São Paulo, Brazil
b
Polytechnic School, Department of Hydraulic and Environmental Engineering, University of Sao Paulo, Sao Paulo, Brazil
c
Center for Natural and Human Sciences, Federal University of ABC (UFABC), São Paulo, Brazil
d
UNESCO Centre for Membrane Science and Technology, School of Chemical Engineering, The University of New South Wales, Sydney, Australia

H I GH L IG H T S

• Electrically conductive PES/PANI/rGO membranes were prepared using phase inversion process.
• PANI and rGO additives improved the membrane conductivity, hydrophilicity and permeability.
• Fouling studies of the PES/PANI/rGO(0.2 g) membranes revealed less propensity to organic fouling.
• Application of external voltage reduced fouling for this electrically conductive membrane.

A R T I C LE I N FO A B S T R A C T

Keywords: A new polyethersulfone (PES) composite membrane using nanostructures of polyaniline (PANI) and reduced
Membrane separation process graphene oxide (rGO) was prepared by the phase inversion process. The investigation focused on the use of PANI
Nanomaterials and rGO as conductive dopants, along with camphorsulfonic acid (HCSA) and dodecylbenzene sulfonic acid
Phase-inversion (DBSA) for PANI preparation. Higher conductivity was obtained for the membrane doped with PANI-DBSA
Fouling
(4.5 ± 0.3 µS·cm−1). The membrane conductivity was further increased to 9.6 ± 0.8 μS·cm−1, 10 times higher
than the conductivity of the PES-control membrane, by incorporating rGO (PES-PANI(DBSA)-rGO(0.2 g). The use
of HCSA as PANI dopant resulted in membranes with higher hydrophilicity compared to the ones obtained with
the PANI-DBSA. The contact angle reduced from 61.9 ± 2.0° (PES-control) to 45.2 ± 1.5° for PES-PANI
(HCSA)-rGO(0.2 g). Moreover, the incorporation of rGO also resulted in fewer but larger macrovoids in the
membranes bottom layer and a roughness (Ra) reduction. More specifically, for PES-PANI(HCSA)-rGO(0.2 g), Ra
dropped to 2.7 ± 0.4 nm when compared to PES membrane control (11.6 ± 3.4 nm). PANI addition sig-
nificantly improved membrane permeability, which was further increased with the addition of rGO. Fouling
studies revealed that the PES-PANI(HCSA)-rGO(0.2 g) membrane featured higher flux recovery ratio (FRR)
(81.3 ± 3.6%) than PES-PANI(DBSA)-rGO(0.2 g) (60.9 ± 5.8%) and PES-control membrane (21.8 ± 5.7%).
After electrochemical cleaning, an additional increase of the flux recovery ratio (FRR) was obtained for con-
ductive membranes. In summary, the composite membranes, specially the HCSA-doped membrane, presented
improved operating performance and fouling mitigation.

1. Introduction number of water treatment technologies developed in recent decades,

the membrane separation process plays an important role for water
Innovative water/wastewater treatment and water reuse technolo- management in urban areas because of the improved treated effluent
gies can offer appropriate solutions to ensure that cities can become quality, small footprint and minimal chemical use [1–3]. However, the
resilient to the challenges of growing water scarcity. Despite a large use of membrane processes for water and wastewater treatment is still

⁎
Corresponding author.
E-mail address: eduardo.subtil@ufabc.edu.br (E.L. Subtil).

https://doi.org/10.1016/j.cej.2020.124612
Received 20 December 2019; Received in revised form 27 February 2020; Accepted 28 February 2020
Available online 29 February 2020
1385-8947/ © 2020 Elsevier B.V. All rights reserved.
E.L. Subtil, et al.
compromised by its high energy consumption and membrane fouling
[4].
Membrane performance depends on the properties of its constituent
materials. In this sense, a very large number of studies have been
aiming to the modification of membranes using anti-fouling materials,
which can change membrane characteristics such as porosity, hydro-
philicity, and roughness [5–7]. In addition, there are many materials
that simultaneously present the potential for fouling mitigation and
conductivity improvement. Such materials have gained attention due to
their great potential to be integrated into electrochemical processes,
particularly when the membrane is used with dual cathode and filtra-
tion functions. In this configuration, the formed electric field has the
potential to mitigate fouling by electrostatic forces which will act di-
rectly onto the membrane surface and pores, creating repulsive elec-
trostatic forces between foulants and membrane, while producing H2O2
on its surface [7–10]. Although the use of conductive membrane re-
presents a technological breakthrough, the use of functional conducting
polymers as additives is still at its beginning.
Polyaniline (PANI) has been intensively investigated as an inter-
esting conductive polymers due to its thermal and chemical stability,
simple polymerization process, easy doping by protonation and low
cost [11–14]. PANI shows conductive and insulating properties, de-
pending on its oxidation state and the protonic species used during the
doping process. Therefore, a promising strategy for producing con-
ductive membranes is doping PANI with long chain organic acids that
possess voluminous apolar tails, such as camphorsulfonic acid (HCSA)
or dodecylbenzene sulfonic acid (DBSA). This strategy improves the
processability, electrical conductivity and solubility of PANI in organic
solvents (e.g. N-methyl-2-pyrrolidone – NMP) used for membrane
casting [15,16].
Other materials have also demonstrated anti-fouling effects [17],
such as metals and metal oxides [18], SiO2, TiO2, Fe3O4, Al2O3 and
ZrO2 nanoparticles [19–22], zeolite [18,23], boehmite [24], carbon
nanotubes (CNT) [25,26], and graphene oxide (GO) [27,28]. Carbon
nanoparticles have attracted attention due to their hydrophilic prop-
erties, which contribute to increased permeability and membrane
contaminant rejection properties. Moreover, these nanoparticles can be
easily modified by incorporating functional groups. Such modification
or functionalization may improve characteristics such as electrical
conductivity and solubility in solvents that are commonly used during
membranes preparation [17]. More specifically, GO features several
oxygen functional groups resulting in favored dispersibility in many
solvents such as water, dimethylformamide (DMF), and NMP [29–31].
Furthermore, the removal of part of these functional groups by reducing
GO to reduced-GO (rGO) provides partial restoration of graphene net-
work, promoting a significant improvement of membrane conductivity
[32,33].
Considering the great potential of membrane fouling reduction by
using diffents nanomaterials, recent studies have evaluated the com-
bination of conductive polymers with other addtives. Zhang et al. [34]
prepared polyvinylidene fluoride (PVDF) membranes using rGO and GO
as additives. PVDF/rGO membranes showed lower flux decay under
electric field as well as higher flux recovery ratio (70%) when compared
to PVDF/GO membrane (64%). According to the authors, the poor flux
and polyacrylamide (PAM) rejection under electrical potential of
PVDF/GO was likely associated with the higher membrane resistivity.
In another study Akin et al. [35] have produced, by the phase inversion
method, polysulfone (Psf)/rGO membranes and Psf/PANI/rGO mem-
branes to improve the salt rejection performance of the nanofiltration
membrane due to the increase in its hydrophilicity. However, the au-
thors did not evaluate the effect of these conductive additives on the
electrochemical properties of the membrane and the potential for mi-
tigating organic fouling, which is quite relevant for membrane appli-
cation.
The synthesis method can also interfere on the membrane con-
ductivity, permeability and selectivity. The most common methods
2
Chemical Engineering Journal 390 (2020) 124612
include formation of the conductive polymer during the preparation of
the support membrane, with polymer matrix-additives mixed solutions
or membrane immersion in polymerization solutions, which allows a
better distribution of conductive polymers in the microporous structure
[36]. However, some methods result in non-uniform deposition of the
conducting polymers, leading to a “swelling” of the membrane affecting
its permeability and selectivity [11]. Many of the conductive mem-
branes found in the literature were prepared via deposition of con-
ductive films over nonwoven support materials [37–43], which can
result in membrane “swelling” and low selectivity.
Despite the studies described above, the preparation of stable con-
ductive membranes remains a challenge [44]. The production of
modified composite membrane using PES and nanostructured additives
of PANI and rGO is recent and requires better understanding, especially
in respect to the impact of PANI doping and rGO concentration on the
membrane properties and fouling mitigation potential. In this context,
the present study focuses on the preparation and characterization of
modified PES composite membranes with PANI/rGO nanostructured
additives. The effect of additives concentration on the morphology,
chemical composition, conductivity, hydrophilicity and permeability
was evaluated. Moreover, the influence of acid dopant, DBSA and HCSA
on the dispersion of the conductive polymer into the PES matrix was
assessed. The potential of organic fouling mitigation due to the addition
of nanoparticles (PANI and rGO) and the foulants removal under ap-
plied voltage were also investigated.
2. Material and methods
2.1. Materials
Reagent grade chemicals have been used. Graphene oxide (GO) was
prepared using a method described elsewhere [45]. Aniline, ammonium
hydroxide (NH4OH, 28%), ammonium peroxydisulfate ((NH4)2S2O8),
APS), N-Methyl-2-pyrrolidone (NMP) (anhydrous, 99.5%) hydrochloric
acid (HCl, 37%), were acquired from LabSynth. The 4-Dodecylbenze-
nesulfonic acid (DBSA, 90%) and 10-Camphorsulfonic acid (HCSA,
98%) were purchased from Fluka Analytical. Polyethersulfone (PES,
Mw: 63,000 g.mol−1) was provided by Solvay. High-purity water was
used in all preparation and membrane tests. For the membrane drying
procedure, isopropyl alcohol (C3H8O, 99.5%) was used. For organic
fouling tests evaluation, humic acid and bovine serum albumin (Sigma
Aldrich) solutions were used.
2.2. Composite membrane synthesis
The PANI was synthesized according the procedure described by
MacDiarmid et al. [13,46]. All membranes used in this study were
prepared as proposed by Maximous et al. [47]. PES neat membranes
were used as a control. Composite membranes were prepared in the
polymer proportions of 90 wt% PES (polymer matrix) and 10 wt%
conductivity additives (PANI and rGO). For PANI doping, two different
acids were evaluated, DBSA and HCSA. Fig. 1 summarizes the propor-
tions of additives used.
PANI-rGO nanocomposites were first obtained by physical mixture
in a fraction of NMP (30 mL), solution A. In a typical experiment, GO
was previously exfoliated in NMP by using the probe sonicator. PANI-
EB was added into the GO dispersions and mixed using a magnetic
stirrer for 24 h. For GO reduction, ascorbic acid were added in a mass
proportion of 10:1 for GO, and the solution was kept stirring for an
additional period of 48 h. The doped state of the nanocomposites was
obtained by adding DBSA and HCSA into PANI-EB-rGO rendering PANI
(DBSA)-rGO and PANI(HCSA)-rGO nanocomposites dispersions, re-
spectively. For comparison, samples with no rGO (i.e., PANI(DBSA) and
PANI(HCSA)) were prepared.
For the casting solution (B), PES was added to the remaining frac-
tion of NMP (50 mL) under mechanical stirring until complete
E.L. Subtil, et al.
Fig. 1. Proportions of each component for the synthesized membranes. For doping PANI 0.94 g of DBSA and 2.3 g of HCSA were added in the casting solution.
solubilization. Then the solutions A was poured into the solution B and
the resulting mixture was stirred for 24 h. Finally, the resulting dope
solution was sonicated by 1.5 h for gas removal. Membrane casting
occurred after two resting hours. The ambient temperature and air
humidity during the synthesis were controlled at approximately 27 °C
and 60%, respectively.
Membrane casting was performed spreading the dope solution over
a glass plate using an automatic film applicator (Elcometer 4340). The
inversion process occurred by the immersion of the glass plate with
polymeric film into the coagulation bath. For removing any residual
solvent trapped into the membrane structure, cast membranes were left
in another high-purity water bath for at least 24 h. For the character-
ization experiments membranes were immersed in isopropyl alcohol for
24 h, and then left to dry. This procedure was used for keeping mem-
branes pore structure integrity.
Because the fraction of PANI and rGO is less than 2% in the poly-
ethersulfone (PES) composite matrix, it was not possible to obtain a
direct view of the physical distribution of PANI and rGO in the mem-
brane. Also, the poor electronic contrast of the components, in this case,
hindered the direct observation of additive (PANI and rGO) assemblies
within the “interior” using SEM imaging techniques.
2.3. Membrane characterization
2.3.1. Spectroscopic studies
X-ray photoelectron spectroscopy (XPS) investigation was carried
out using a ThermoFisher Scientific K-alpha + spectrometer. For
UV–vis analysis, the spectra were collected in the range of
200–1100 nm and the dispersion samples (50 µL) were diluted in 4 mL
of NMP. Raman spectroscopy was carried out using a Raman Renishaw
inVia spectrometer and a solid-state laser operating at a wavelength of
785 nm.
2.3.2. Resistivity and conductivity
Membrane conductivity was measured according to the ASTM
D4496-13 standard [48]. A test cell and a digital megohmmeter were
also used. (Minipa MI-2552). The specimen (12 × 2.6 cm) was placed
in the test cell between two copper plates (electrodes). Its entire length
was in contact with the plates. Voltages of 100 V, 500 V and 1000 V
were then applied, and each corresponding resistivity was noted. The
procedure was carried out for distances of 5 and 10 cm between elec-
trodes. From the resistance results R (Ω cm−1), a global mean resistivity
ρ (MΩ cm−1) and conductivity δ (μS cm−1) were calculated using Eqs.
(1) and (2), considering the distances between electrodes L (cm) and
the sample width B (cm). The electrical resistance measurements were
performed with wet membranes and five samples of each synthesized
membrane were used in each test.
B
ρ = R∙
L (1)
3
Chemical Engineering Journal 390 (2020) 124612
1
δ=
ρ (2)
2.3.3. Membranes morphology
Scanning electron microscopy (SEM) – FEI Quanta 250 – was used to
obtain the membranes cross-section images. The membranes were
broken after its immersion in liquid nitrogen to maintain the membrane
porous structure integrity. Membrane thickness, active separation layer
thickness and the number of fingers (elongated internal pores) in 50 µm
of membrane length were measured using the software ImageJ®. The
membrane surface roughness was evaluated using an atomic force mi-
croscopy (AFM – Bruker Dimension ICON SPM).
Membrane porosity (P) were estimated using Eq. (3), reported on a
previous study [49]. The porosity is associated with the membrane
resistance for water transport. Denser membranes, related with lower
porosity, or void volumes, are expected to present higher resistance for
water transport. In that sense, membranes with higher porosity will
facilitate the water transport, which makes the porosity measurements
an reasonable indicator for membrane internal morphology. First, wet
membrane thickness and area were measured. The membrane thickness
was estimated by five measurements using an electronic micrometer
(Digimess, 0–25 mm 0.001 mm). Second, each sample was placed be-
tween tissues to remove free water from its surface and after that
weighed. Finally, the membranes were submitted to the drying proce-
dure described in Section 2.2 and weighed again.
m1 − m2
ρw
P(%) = ∙100
Vm (3)
where m1 is the membrane wet weight, m2 is the membrane dry weight,
ρw is the specific density of water and Vm is the membrane volume
obtained from the thickness (m) and area (m2).
2.3.4. Contact angle
The hydrophilicity of the synthesized membranes was estimated by
contact angle analysis (Kino model SL150). The dried samples were
placed on glass plates (6 × 2 cm), and high-purity water droplets were
dripped under the sample with the aid of a needle (0.2 µm). After 1 min,
the contact angle was read. Three samples from each membrane were
used and 5 measures of each sample were performed. The significance
of these results was evaluated using the Kruskal-Wallis Test (ANOVA,
non-parametric) in the Action Stat®, to test whether there was a sig-
nificant difference between the contact angles of membranes at the
significance level of 5%, p-value less than 0.05. As the Kruskal-Wallis
test only indicates if there is at least one difference between the contact
angles of the analyzed membranes, the multiple comparisons procedure
with the Simes-Hochberg method was also performed to identify which
pairs of membranes presented a contact angle significantly different at
the significance level of 5%.
E.L. Subtil, et al. Chemical Engineering Journal 390 (2020) 124612

2.3.5. Membrane permeability Jp ⎞

rt = ⎛1 −
⎜ ⎟ ∙100
The permeability of the synthesized membranes was obtained using ⎝ Jw1 ⎠ (6)
the procedure described by Morihama and Mierzwa [50]. For this
purpose, a tangential flow test cell was fed with high-purity water, Jw2orw3 − Jp ⎞
rr = ⎛ ∙100
producing a permeate flow for a certain time. For each type of mem-
⎜ ⎟

⎝ Jw1 ⎠ (7)
brane synthesized, three permeability tests were performed. Each
sample had 13 × 9 cm with a total filtration area of 117 cm2. J − Jw2orw3 ⎞
rir = ⎛ w1
⎜ ∙100
⎟

⎝ Jw1 ⎠ (8)

2.4. Organic fouling experiment

3. Results and discussion
Fouling behavior was analyzed in a dead-end stirred cell (Amicon
8400, 400 mL) (Fig. 1S – supplementary material). The system was 3.1. Effect of PANI, rGO and dopant acid on membrane composition and
pressurized with nitrogen gas and operated at a pressure of 1 bar and a conductivity
stirring speed of 580 rpm. During the experiments, the temperature was
kept at 23 °C. Spectroscopy analyzes were performed to study the incorporation of
Before starting the tests, the membranes were compacted for 20 min PANI and rGO into the PES matrices. Fig. 3a shows the survey spectra of
at 1 bar. The high-purity water flux Jw1 (L.m−2.h−1) was estimated by PES and PES-PANI-rGO membranes in addition to their corresponding
Eq. (4). surface element atomic percentage. The results of the survey spectra
indicate that membranes with PES only have carbon and oxygen as the
V primary elements. On the other hand, nitrogen peak was visible on the
Jw1 =
A∙Δt (4) PES-PANI-rGO membrane spectra due to PANI incorporation. Further-
more, the increase of sulfur atomic percentage could be credited to the
where V (L) is the permeate volume, A (m2) is the membrane area and
dopant acids used during PES-PANI-rGO dispersions preparation. The
Δt (h) is the time. After measuring the Jw1, the stirred cell was refilled
high-resolution XPS spectrum of C1s core-level of GO (Fig. 2b) can be
with the model fouling solution composed of 1 mg.L−1 of humic acid
deconvoluted into five peaks corresponding to sp2 hybridized carbon
(HA) and 60 mg L−1 of bovine serum albumin (BSA). A mixed model
(283.6 eV), sp3 hybridized carbon (284.6 eV), epoxy/hydroxyl groups
solution was used to expose the membrane to a severe and re-
(CeO, 286.7 eV), carbonyl (C]O, 287.8 eV) and carboxylates (OeC]
presentative condition that could occur in a full-scale application and
O, 288.6 eV) groups [51,52]. The C1s spectrum of PES (Fig. 3c) shows
not to evaluate the interaction of the membrane individually with the
deconvoluted peaks at 284.6 eV and 286.4 eV associated with char-
main organic foulants. A mixed model solution was used to expose the
acteristics CeC and CeO components of the PES chain, respectively
membrane to a severe and representative condition that could occur in
[53]. The C1s core-level spectra of the resulting PES-PANI(HCSA)-rGO
a full-scale application and not to evaluate the interaction of the
(0.2 g) (Fig. 3d) and PES-PANI(DBSA)-rGO(0.2 g) (Fig. 3e) show four
membrane individually with the main organic foulants. The flux for
curve-fitted peaks. Besides CeC and CeO components, peaks corre-
model fouling solution Jp (L.m−2.h−1) was measured. Then, the
sponding to CeN, C]N+ and C]O species are observed attributable to
membrane was physically cleaned with high-purity water and another
PANI and rGO incorporation [54,55]. In addition, a π-π* transition
permeation test was performed with high-purity water to obtain the
band characteristic of shake-up satellites in aromatic systems can be
membrane flux Jw2 (L.m−2.h−1). Only for the electrically conductive
seen above 290 eV [56]. It is worthwhile to note a stronger change of
membranes, PES-PANI(DBSA)-rGO(0.2 g) and PES-PANI(HCSA)-rGO
components binding energies in PES-PANI(DBSA)-rGO(0.2 g) to lower
(0.2 g), an electrochemical cleaning test was carried out.
energies, which suggests a strong interaction between the polymers and
For the electrochemical cleaning the electrochemical cell used was
rGO likely due to DBSA acid dopant favoring their dispersion.
composed of an external source connected to two stainless steel screens,
The effect of the acid dopant was also evaluated from the N1s core-
one being used as contact for the electro-conductive membrane (Fig. 2).
level spectra of the membranes (Fig. 4). Curve-fitted N1s spectrum of
The cell was submerged in an electrolyte solution (sodium sulfate –
PES-PANI(HCSA)-rGO(0.2 g) (Fig. 4a) shows the quinoid imine (eN]),
30 mg·L−1). An electrical potential of 5v was applied for 10 min for
benzoid amine (eNHe), and charged nitrogen (N+) peaks located at
foulants removal, which was accomplished by electrochemical oxida-
398.5, 399.6 and over 400.6 eV, respectively [54,55]. In addition, PES-
tion, electrostatic repulsion and formation of nanobubbles on the
PANI(DBSA)-rGO(0.2 g) (Fig. 4b) exhibited N1s spectrum deconvoluted
membrane surface. After the electrochemical cleaning, the membrane
into two peaks assigned to the benzoid amine (eNHe) at 399.5 eV and
was physically cleaned again with high-purity water and another per-
the cationic nitrogen atoms (N+) at 400.4 eV. Thereby, N1s spectrum of
meation test was performed using high-purity water to obtain the
PES-PANI(DBSA)-rGO(0.2 g) suggests that all the imine nitrogen atoms
Flux recovery ratio (FRR) approach was used to evaluate the fouling
are completely protonated which is consistent with the fact that pro-
mitigation potential of the membranes [35], according to Eq. (5). In
tonation occurs preferentially at the imine nitrogen atoms [55]. These
addition, the total (rt), the reversible and irreversible fouling ratios
spectra indicate a higher degree of protonation for the membrane
were also calculated with the Eqs. (6), (7) and (8), respectively.
prepared by using the DBSA dopant, which results in better dispersion
of PANI during membrane preparation. It is also interesting to point out
J
FRR = ⎛ w2orw3 ⎞ ∙100
⎜ ⎟ that both N1s spectra (Fig. 4a, b) show stronger relative intensity of the
⎝ Jw1 ⎠ (5) benzoid component (eNHe), which is likely to be associated with a
reducing process of the PANI, due to the ascorbic acid reducing agent
employed for GO reduction.
The higher degree of reduction for PANI into the membranes was
evaluated by the UV–Vis spectra. Fig. 4c displays the UV–Vis spectra of
PANI dispersion in NMP during the different preparation steps before
adding it to PES. PANI-EB and PANI-GO spectra exhibit the character-
istic bands of the emeraldine-base form, showing π-π* transition at
~330 nm and band attributed to a local charge transfer between a
Fig. 2. Schematic diagram of electrochemical cleaning. quinoid ring and the adjacent imine–phenyl–amine units at ~630 nm.

4
E.L. Subtil, et al. Chemical Engineering Journal 390 (2020) 124612

Fig. 3. (a) Survey XPS spectra of PES and PES-PANI-rGO membranes. XPS spectra of C1s for: (b) GO; (c) PES membrane; (d) PES-PANI(HCSA)-rGO(0.2 g) and (e) PES-
PANI(DBSA)-rGO(0.2 g).

By adding the ascorbic acid to reduce GO (PANI-EB-rGO), a stronger
relative-intensity of π-π* transition band can be seen, whereas the band
at 630 nm is no longer visible. These results indicate a concomitant
reduction of GO and PANI during dispersion preparation [57]. The
following doping by acid (PANI(HCSA)-rGO(0.2 g)) results in an
emerging polaron-π* band at ~440 nm (Fig. 4c-Insert). For comparison,
UV–vis spectrum of PANI(HCSA) sample prepared with no content of
rGO shows the characteristics bands of emeraldine salt form with po-
laron-π* band at ~440 nm and the free-carrier tail starting from
~850 nm to the infrared region.
Fig. 5 exhibits the Raman spectra of PES and PES modified mem-
branes with PANI-rGO additives. The PES modified membranes show
the characteristic peaks corresponding to the emeraldine form of PANI.
The PES-PANI-rGO spectra show peaks at 1604 cm−1 due to CeC
stretching vibration of the benzoid units and a shoulder at 1520 cm−1
related to the C]C stretching vibration in the quinoid ring of the
conducting polymer. In addition, PES modified membranes spectra also
exhibit a strong band at 1389 cm−1 corresponding to CeN+ vibrations

Fig. 4. XPS spectra of N1s for: (a) PES-PANI(HCSA)-rGO(0.2 g) and (b) PES-PANI(DBSA)-rGO(0.2 g). In (c): UV–Vis spectra of the different steps carried out to obtain
PANI(HCSA)-rGO(0.2 g) dispersion in NMP.

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E.L. Subtil, et al. Chemical Engineering Journal 390 (2020) 124612

measured (Fig. 6). Superior conductivity was obtained for PANI-DBSA

(4.5 ± 0.3 µS·cm−1), which was almost four times greater than to the
membrane whose PANI was doped with HCSA (1.3 ± 0.1 µS·cm−1).
The better conductivity obtained for the membranes with PANI-DBSA is
likely resulting from the higher degree of protonation of the conducting
polymer by the DBSA dopant (Fig. 3b). Moreover, the presence of a long
aliphatic and nonpolar chain (dodecyl) of DBSA is responsible for su-
perior interaction between the dopant acid and the PES polymeric
matrix [61]. This behavior enhanced the dispersion of PANI into the
PES matrix, resulting in a large number of interconnects between PANI
nanoparticles.
Fig. 6 also exhibits the effect of rGO concentration on the membrane
conductivity. The presence of rGO increased the membrane con-
ductivity to 6.7 ± 0.3 μS·cm−1 (PES-PANI(DBSA)-rGO(0.05 g) and
2.8 ± 0.1 μS·cm−1 (PES-PANI(HCSA)-rGO(0.05 g). Moreover, by
raising the rGO concentration, the membrane conductivity reached
9.6 ± 0.8 μS·cm−1 for PES-PANI(DBSA)-rGO(0.2 g), which corre-
sponds to more than 10 times the conductivity of the PES control
membrane (0.63 ± 0.01 μS·cm−1). The partial removal of functional
oxygen groups from GO by reducing agents provides partial restoration
of the graphene network improving the membrane conductivity, which
is especially important to enable its use in electrochemical fouling
mitigation processes [32,33].
In a similar approach proposed by Liu et al. [62], polypyrrole (PPy)
and sodium dodecyl benzene sulfonate (SDBS) were used to improve
the conductivity of polyvinylidene fluoride (PVDF) membrane by phase
inversion method. The authors obtained approximately 0.6 MΩ·cm−1 of
resistivity in the best case (with SDBS and 10 wt% of PPy), which was
six times higher than the best case presented this study (0.1 MΩ·cm−1).

Fig. 5. Raman spectra of PES and modified PES membranes (wavelength of

785 nm). 3.2. Effect of PANI, rGO and dopant acid on morphology, hydrophilicity
and permeability of modified membranes

of the delocalized polaronic units and a shoulder at 1251 cm−1 (C-N

Fig. 7 exhibits the cross-sectional SEM images obtained for the PES
stretching vibrations). The band at 1182 cm−1 with a shoulder at
control and composites membranes. Morphological analyses show that
1150 cm−1 is associated with CeH bending vibrations of the benzoid
all prepared membranes present asymmetric internal structures: selec-
and semi-quinoid units [58,59]. It is important to mention that the D
tive layer on the top surface and elongated finger-like pores extending
and G bands attributed to rGO at about 1335 and 1583 cm−1, respec-
over the membranes thickness. These membrane characteristics are
tively [60], are likely overlapped by the characteristic PANI fluores-
summarized in Fig. 8. The addition of PANI and rGO had a significant
cence. Similar behavior were observed for PANI-CNT nanocomposites
effect on the morphology of the modified membranes. The first one
where characteristic bands related to CNT could be visualized only at
refers to the number of finger-like pores of the membranes, which were
50 wt% CNT concentration [58].
higher and relatively thinner in the PES membrane, compared to the
In order to investigate the effect of PANI with different acid dopants
ones of the membranes cast with addition of PANI and rGO (Fig. 7a).
and rGO, the conductivity and resistivity of modified membranes were
The greatest reduction on the number of finger-like pores occurred with

Fig. 6. Average resistivity (a) and conductivity (b) for control and composite membranes.

6
E.L. Subtil, et al. Chemical Engineering Journal 390 (2020) 124612

Fig. 7. Scanning electron microscopy for: a) PES control, b) PES-PANI(HCSA), c) PES-PANI(HCSA)-rGO(0.05 g), d) PES-PANI(HCSA)-rGO(0.2 g), e) PES-PANI(DBSA),
f) PES-PANI(DBSA)-rGO(0.05 g) and g) PES-PANI(DBSA)-rGO(0.2 g).

the addition of rGO in the matrix, especially for those membranes
doped with DBSA with the addition of 0.2 g of rGO, with the transistion
to sponge-like pore structure. However, in such cases, the finger-like
pores are slightly wider than that of the PES membrane (Fig. 7). Ad-
ditionally, Fig. 8b exhibits the increase of the membrane skin layer
thickness due to the incorporation of the additives. The most significant
change can be observed for PES-PANI(DBSA)rGO(0.2 g) (Figs. 7g and
8b) which shows the largest membrane surface thickness
(6.4 ± 0.5 µm) when compared to PES (1.5 ± 0.2 µm). Furthermore,
it could be observed in the cross-sectional SEM images (Fig. 7b, e) that
the selective layer of PANI(DBSA) membrane seems to be denser and
more homogeneous compared to the selective layer of the PANI(HCSA)
membrane, which, as previously discussed, could be a result of en-
hanced dispersion of PANI-DBSA into PES matrix. However, it is in-
teresting to point out that the addition of rGO, apparently, reduced the
rejection capacity of the PES-PANI(DBSA)-rGO (Fig. 7f, g), because its
selective layer seems to be less dense in comparison to the ones of other
membranes.
The mechanism of finger-like or sponge-like internal pore structure
formation is strongly determined by the water-induced phase inversion

Fig. 8. a) Numbers of fingers macrovoids and b) surface thickness and roughness of PES and PES composite membranes.

7
E.L. Subtil, et al.
Fig. 9. Atomic force microscopy for PES and composite membranes.
process. In this study, the incorporation of rGO and dopant acids,
particularly DBSA, increases the viscosity of the casting solutions af-
fecting the phase inversion process. Highly viscous dope solutions tend
to exhibit reduced diffusion rate between the solvent and the non-sol-
vent in the sublayer. As a result, a rapid demixing in the upper layer and
slow precipitation in the sublayer may occur leading to the formation of
a small number of large sized finger-like pores into the sublayer
[63,64]. This behavior could clearly be seen for most of the cast
membranes, except for the PES-PANI(DBSA)-rGO(0.2 g) membrane
(Fig. 7g), where the number of finger-like pores were expressively
suppressed, indicating a rapid de-mixing process during the phase in-
version process through all membrane extension, resulting in a sponge-
like pore structure. This phenomenon is associated with the differences
on chemical activities of the dope solution and nonsolvent during the
phase inversion process, as it was pointed out in a previous work [65].
The surface roughness of the PES and modified composite mem-
branes was investigated using AFM measurements (Fig. 9). The average
roughness (Ra) of the respective membranes is summarized in Fig. 8b.
Compared with the PES membrane (Ra of 11.6 ± 3.4 nm), the addition
of PANI in the polymer matrix resulted in decrease of Ra to 9.7 ± 3.4
and 6.7 ± 3.4 nm for PES-PANI(HCSA) and PES-PANI(DBSA), re-
spectively. Interestingly, when rGO was added, an opposite behavior
was observed on the surface roughness for PANI(HCSA) and PANI
(DBSA) membranes (Fig. 8b). With the increase in the rGO content, the
Ra decreased for PES-PANI(HCSA)-rGO membranes, reaching
2.7 ± 0.4 nm with the highest amount of rGO (0.2 g). Previous studies
have reported that low electrostatic interaction can result from the use
of low concentrations of modified carbon nanoparticles, as they are
8
Chemical Engineering Journal 390 (2020) 124612
frequently embedded into the membranes structure resulting in
smoother membrane surfaces [27,66–68]. However, by raising the rGO
content in the samples prepared with PANI(DBSA), an increase of Ra
could be observed reaching 12.1 ± 4.1 nm for PES-PANI(DBSA)-rGO
(0.2 g) which is even higher than that observed for the PES membrane
only (11.6 ± 3.4 nm). During the preparation of composite mem-
branes by phase inversion process, nanoparticles tend to agglomerate
spontaneously on the membrane surface in order to reduce the interface
energy [23]. In this study, the increased viscosity of the casting solution
due to the use of DBSA may have hindered the dispersion of rGO na-
noparticles promoting their aggregation on the surface (Fig. 9e, g)
leading to rougher membrane surfaces.
The membrane surface hydrophilicities were evaluated by water
contact angle measurements (Table 1). The incorporation of PANI ad-
ditives resulted in decrease of the contact angles which is likely re-
sulting from the intrinsic hygroscopic property of HCSA and DBSA acid
dopants. The contact angle was further decreased after addition of rGO.
The most significant reduction was observed for PES-PANI(HCSA)-rGO
(0.2 g) (45.2 ± 1.5°) suggesting the strongest surface hydrophilicity. In
addition, it is interesting to point out that PES-PANI(DBSA)-rGO(0.2 g)
shows slight larger contact angle than the sample prepared with 0.05 g
which may be explained by the higher roughness presented for the
former one. The intrinsic value of contact angle can be significantly
disturbed by roughness and hydrophilic groups on membrane surface.
In most cases, roughness increases the amount of trapped air on the
membrane surface and consequently results in higher water contact
angle [49]. In contrast, the combination of a smoother membrane
surfaces (Fig. 9b, e and F) and the presence of hydrophilic functional
E.L. Subtil, et al. Chemical Engineering Journal 390 (2020) 124612

Table 1
Average contact angle, permeability and porosity for PES and composite membranes.
Membrane Contact angle (°) Permeability (L·m−2·h−1·bar−1) Porosity (%)

PES-control 61.9 ± 2.0 69 ± 12 61.1 ± 5.5

PES-PANI(HCSA) 55.9 ± 1.9 118 ± 20 65.2 ± 1.0
PES-PANI(DBSA) 56.9 ± 1.7 174 ± 28 67.1 ± 1.6
PES-PANI(HCSA)-rGO(0.05 g) 52.4 ± 1.8 154 ± 22 74.6 ± 1.8
PES-PANI(DBSA)-rGO(0.05 g) 53.4 ± 1.9 179 ± 15 71.5 ± 3.9
PES-PANI(HCSA)-rGO(0.2 g) 45.2 ± 1.5 227 ± 27 74.9 ± 4.3
PES-PANI(DBSA)-rGO(0.2 g) 54.4 ± 1.6 344 ± 24 71.4 ± 4.6

groups from rGO may have been the key factor in reducing the contact
angle for PES-PANI(HCSA)-rGO membranes.
Table 1 also shows the effect of the additives nanomaterials on the
permeability of the membranes for pure water. It is worthwhile to note
that for all synthesized composite membranes, there was a significant
increase of permeability. The incorporation of PANI nanostructures
resulted in the increase of membrane permeability of about 70% (PES-
PANI(HCSA)) and 150% (PES-PANI(DBSA) when compared to PES
membrane. The membrane permeability was further increased after
addition of rGO reaching 344 ± 24 L·m−2·h−1·bar−1 for PES-PANI
(DBSA)-rGO(0.2 g), which is almost 5 times greater than the value
obtained for the PES control.
Similar trend was observed for the porosity characteristics of the
composites membranes (Table 1). The addition of PANI and rGO na-
nostructures resulted in increase of porosity which is explained by the
increased size of finger-like pores formed in the membrane sublayer, as
shown in Fig. 7. Thereby, the enhanced permeability of the composite
membranes is likely resulting from the double effect of increased
combination of membrane hydrophilicity and porosity (Table 1), which
reduced the resistance for water transport. Hydrophilicity property can
influence water permeability due the interactions between water mo-
lecules and membrane pore surface, contributing to larger uptake of Fig. 10. Normalized flux versus permeate volume for PES and composite
water molecules by the membrane and promoting higher membrane membranes during model solution filtration. Two replicates were reported.
wettability. However, it is important to note that the increment in the
permeability of the PES-PANI(DBSA)-rGO(0.2 g) membrane was sig- (Fig. 10). For these samples, there was no significant flow decay at the
nificantly greater than that observed for the PES-PANI(HCSA)-rGO beginning of filtration test, especially for PES-PANI(HCSA)-rGO(0.2 g)
(0.2 g) membrane. This may be associated not only with a change of the which showed slight flow reduction only when approximately 100 mL
internal membrane morphology and hydrophilicity, but also with the of the foulant model solution (containing BSA and HS) had already been
presence of a less dense and more porous skin layer for the former one filtered. At the end of the same recovery rate, 88 and 91% of the
(Fig. 9g). permeate flux was maintained for PES-PANI(DBSA)-rGO and PES-PANI
(HCSA)-rGO membranes, respectively. The membrane characteristics
such as hydrophobicity and roughness play an important role in the
3.3. Organic fouling interaction and electrochemical fouling removal
initial deposition of species over the membrane surface. Considering the
hydrophobic nature of protein and humic substances, smoother and
The membranes with the most promising characteristics, i.e. PANI
more hydrophilic membranes are required to mitigate initial fouling
(DBSA)-rGO(0,2g) and PANI(HCSA)-rGO(0,2g), were selected for
tendencies. In general, hydrophilic membranes delay the adsorption of
fouling evaluation tests, due to their significant improvements in con-
organic foulants, due to the formation of a water layer on their surfaces
ductivity, hydrophilicity and permeability.
[27]. Furthermore, it is known that membranes with smoother surface
Fig. 10 shows the results for flow decay as a function of permeate
present better antifouling capacities, due the lower potential to foulants
volume for the selected membranes. For PES membrane, a marked re-
attachment [70–75]. These characteristics may have been responsible
duction of the permeate flow was observed at the beginning of filtration
for the high anti-fouling capacity achieved by PES-PANI(HCSA)-rGO
test followed by a steady decrease of the flow decay resulting in only
membrane, given its greatest hydrophilicity (Table 1) and lowest
51% of the initial permeate flow being maintained at the end of the
roughness (Fig. 8b). SEM images of the clean and fouled PES and PES-
experiment. In general, an intense decline of the initial flow in porous
PANI(HCSA)-rGO membranes can be seen in the supplementary mate-
membranes rejecting humic substances and proteins, as observed for
rial (Fig. 3S), in which it is possible to observe a slight change on their
the PES membrane, is more strongly related to the high flow resistance
surfaces, the fouled membranes seem to have smooth surfaces.
imposed by small particles adsorbed in the pores than the resistance
In addition to the flow decay, reversible and irreversible fouling
induced by cake layer formation [67,68]. This may be associated to the
ratio was used to quantitatively investigate the fouling mechanisms of
greater interaction between the foulants (humic substances and pro-
the membranes. As expected, a significant reduction in the total fouling
tein) and the PES membrane consisting in one of the main drawback of
ratio was observed for the composite membranes (Fig. 11). The use of
using this material, since hydrophobic surface will induce a rapid ad-
PANI and rGO additives was responsible for reducing the total fouling
sorption of these substances by the membrane during the solution fil-
ratio from 84 ± 2% (PES) to 49 ± 5% and 22 ± 4% for PES-PANI
tration [69].
(DBSA)-rGO and PES-PANI(HCSA)-rGO membranes, respectively.
On the other hand, a positive effect on fouling prevention was noted
However, the reversible fouling value was significantly lower than the
for the modified membranes with PANI and rGO nanostructures

9
E.L. Subtil, et al.
Fig. 11. Quantitatively estimated fouling for PES and composite membranes
after organic fouling. Two replicates were reported.
irreversible fouling for all evaluated membranes implying that the latter
plays a major role on the total fouling (Fig. 11). These results indicate
that most of the adsorbed species on the membrane surfaces were not
removed by simple physical cleaning with use of water. Therefore, the
high FRR results achieved for PES-PANI(HCSA)-rGO (81%) and PES-
PANI(DBSA)-rGO) (61%) are strongly related to the intrinsic potential
of the composite membranes in preventing deposit formation rather
than its ability to remove adsorbed species by using only physical water
cleaning.
In order to demonstrate the durability of antifouling property of the
membrane, three filtration cycles were carried out with the best-per-
forming membrane. It could be seen from Fig. 12 the great potential for
fouling mitigation of PES-PANI(HCSA)-rGO membrane in the three
cycles where FRR were 84.5%, 80.8% and 78.9%, respectively asso-
ciated to initial water flux.
The organic fouling removal potential of the conductive modified
membranes was also assessed by electrochemical cleaning procedure
(Fig. 11). It was observed an additional increase of the FRR for the
conductive membranes indicating desorption of heavier fouling from
the membrane. In respect to the irreversible fouling after the physical
water cleaning, the electrochemical procedure was able to increase
FRR, I.e. ( (Jw1 − Jw2) − (Jw1 − Jw3)
Jw1 − Jw2 ), by 34% and 19% for PANI(HCSA)-rGO
(0.2 g) and PANI(DBSA)-rGO(0.2 g) membranes, respectively. Conse-
quently, the electrochemical cleaning contributed with an overall FRR
Fig. 12. Recycling characteristics of PES-PANI(HCSA)-rGO membrane during
model solution filtration.
10
Chemical Engineering Journal 390 (2020) 124612
of 7.3 ± 0.1% for PANI(DBSA)-rGO(0.2 g) and 6.2 ± 0.6% for PANI
(HCSA)-rGO(0.2 g).
Fouling removal using electro-conductive membranes occurs con-
currently with several mechanisms associated with direct and indirect
electrochemical oxidation at a given potential, electrostatic desorption
and nanobubble formation on the membrane surface. Given the short
period of time (5 min) related with the applied potential during
cleaning, nanobubble formation and eletrostatic repulsion may have
been the main mechanisms of foulant desorption. Nanobubbles form
between the membrane and the fouling layer, so that the adsorbed
particle is forced to separate from the solid-liquid interface and migrate
to the liquid-vapor interface during bubble growth. Once at the liquid-
vapor interface, the particle can be easily removed by low shear water
flow or the presence of an electrochemical field [76,77]. In addition,
electrostatic repulsion is expected to be responsible for foulants de-
tachment because of their specific eletrical charge.
Regarding the structural integrity of the membranes after electro-
chemical cleaning, the membranes were subjected to another filtration
test with deionized water (Jw3), as it can be seen in Fig. 3S of the
supplementary material. During this test, a flow behavior similar to Jw2
and Jw1 (both performed with deionized water) was observed. In ad-
dition, Jw3 (259.2 ± 2.9 L/m2.h and 93.4 ± 3.8 L/m2.h for PES-PANI
(DBSA)rGO and PES-PANI(HCSA)rGO membranes, respectively) was
significantly lower than Jw1 (382.1 ± 35.7 L/m2.h and 106 ± 6.0 L/
m2.h for PES-PANI(DBSA)rGO and PES-PANI(HCSA)rGO, respectively),
indicating that there was no apparent disruption of the selective
membrane layer. A SEM image of the membrane cross-section was
obtained after electrochemical cleaning and it was not observed any
significant change in the internal structure of the conductive mem-
branes (Fig. 4S – supplementary material).
The rejection capacity of the membranes during the fouling test was
also evaluated. Fig. 13 demonstrates a high selectivity characteristic for
PES-PANI(HCSA)-rGO membrane (93 ± 0.3% of total organic carbon
rejection), whereas a significant reduction in rejection capacity was
observed for the PES-PANI(DBSA)-rGO (36 ± 0.9% of TOC rejection).
The rejection and flow performances strongly depend on the chemical
structure of the membrane active layer as well as their surface char-
acteristics where solute separation occurs. In this sense, the increase in
viscosity due to the use of DBSA associated with the presence of larger
amounts of rGO led to the formation of a more porous selective layer for
PES-PANI(DBSA)-rGO membrane promoting high membrane perme-
ability, but a relatively lower rejection capacity. On the other hand, the
combination of PANI-HCSA and rGO led to the formation of a thicker
and denser selective layer resulting in high rejection capacity.
Fig. 13. Total organic carbon (TOC) in the model solution and rejection ca-
pacities for PES and composite membranes.
E.L. Subtil, et al.
4. Conclusions
A novel conductive PES-PANI-rGO membranes have been success-
fully fabricated by phase inversion process. The results showed that the
type of doping acid used for protonation of PANI has a great influence
on the conductivity of membranes, as well as the addition of rGO.
Furthermore, significant changes in membrane morphology were ob-
served with the use of these nanomaterials. In general, such modifica-
tions led to increased permeability, porosity and hydrophilicity, espe-
cially for membranes that were synthesized with PANI-HCSA. These
membranes characteristics revealed significant impact on the anti-
fouling properties for the composite membranes. All modified mem-
branes demonstrated less propensity to organic fouling, particularly for
PES-PANI(HCSA)-rGO which showed highest fouling reduction poten-
tial and highest rejection capacity. Nevertheless, no reduction in irre-
versible fouling associated with water cleaning was observed.
The electrochemical cleaning strategy for fouling removal is in-
novative and, in this study, showed to be attractive for removal of re-
maining foulants from the membrane after physical cleaning. It is
worthwhile to mention that this additional removal strategy was only
possible due to the improved conductivity of the modified membranes,
which is especially important to enable their use in electrochemical
fouling mitigation processes.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
This work was supported by the São Paulo Research Foundation
(FAPESP) (Grant number: 2016/23684-0). WAA is supported by the
National Council for Scientific and Technological Development (CNPq
grant no. 302923/2015-2), the National Institute of Science and
Technology in Bioanalytics (FAPESP grant no. 2014/50867-3 and CNPq
grant no. 465389/2014-7), and the São Paulo Research Foundation
(FAPESP grant no. 2017/02317-2). ECV and HGL are supported by
FAPESP (process number 2011/16615-9) and CNPq (process number
481647/2011-2) and CAPES The authors are also grateful to the
Multiuser Central Facilities of UFABC and UNESCO Centre for
Membrane Science and Technology for the experimental support.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cej.2020.124612.
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