Journal of Membrane Science 429 (2013) 252258

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Journal of Membrane Science

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

Conductive and hydrophilic polypyrrole modied membrane cathodes

and fouling reduction in MBR
Lifen Liu a,b,n, Jiadong Liu a, Gao Bo a, Fenglin Yang a, John Crittenden b, Yongsheng Chen b
a
Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), School of Environmental Science and Technology, Dalian University of Technology,
Dalian 116024, PR China
b
School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, Georgia, USA

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

Article history: For increasing separation efciency and reducing energy consumption, study about membrane fouling
Received 28 March 2012 reduction has ever been a hot topic. To prepare fouling-resistant, hydrophilic and conductive
Received in revised form membrane, polyester lter cloth was modied with polypyrrole (PPy) in-situ formed by polymerization
20 November 2012
of pyrrole (concentration 3.868 g/L) and sodium dodecyl benzene sulfonate (SDBS). Increase in SDBS
Accepted 25 November 2012
concentration (0.5, 1 or 2 g/L) during polymerization increased the membrane electric conductivity and
Available online 3 December 2012
hydrophilicity, and enhanced the permeate ux and anti-fouling properties of modied membrane.
Keywords: A voltage drop at 0.2 or 0.4 V/cm exhibited better fouling reduction than 0 V/cm. In the long-term
Membrane fouling ltration tests with the PPy (2 g/L SDBS) modied membrane, both the irreversible and the total
Membrane bioreactor
resistances were decreased (5 times and  2 times, respectively) by applying 0.2 V/cm electric eld,
Conductive membrane
indicating the effect of applied electric eld towards fouling reduction. The membrane cathode
Polypyrrole
Electric eld successfully prevented the pore clogging.
& 2012 Elsevier B.V. All rights reserved.

1. Introduction
Electric elds have been used in membrane fouling reduction for
approximately 50 years [1], the operating principles were the
electrophoresis and electrostatic repulsion, and the forces exerted
by electric elds on the charged particles were used to inhibit fouling.
Though highly energy consumptive, it was used in separation of
proteins, anion/polymers (voltage drop 167 V/cm), fruit juices (vol-
tage drop 38 V/cm) and micelles (voltage drop 10 V/cm) [24]. As
the applied voltage was high and corrosion resistant anode material
(such as titanium or which coated with noble metal such as
platinum) was required but expensive, the commercial implementa-
tion of electric-eld-enhanced technologies [5] was limited. The
effectiveness of using an electric eld to maintain the ux of a
membrane bioreactor had been reported [68], but all these tests
needed an individual cathode other than the membrane itself, which
increases reactor volume. Fouling reduction (16%) in MBR in one case
involved electro-coagulation [8] which was separately operating in a
zone away from the membranes, and the electric potential was not
directly applied on the membrane.
The most effective way to control membrane fouling using electric
eld/electrodes and membrane (i.e., a conductive membrane) in
n
Corresponding author at: No. 2, Linggong Road, Dalian University of Technol-
ogy, Dalian, PR China. Tel.: 86 411 84706173; fax: 86 411 84708083.
E-mail address: yuzhe25521@yahoo.com.cn (L. Liu).
membrane bioreactor (MBR) is making the electric eld work against
fouling, pushing the pollutant away from the membrane surface
directly. We previously tested this idea by implanting an array of
parallel microelectrodes inside a membrane module to simulate a
membrane cathode. Using both nonwoven polypropylene and lter
polyester membranes, this design prevented colloidal membrane
fouling effectively [9]. The carbon cloth also had been used in
applying intermittent electric eld for fouling suppression [10].
Another study showed the feasibility of fouling reduction using a
negative dielectrophoretic force from an AC power source [11].
When a conductive polymer membrane is used as the cathode,
the electric eld can make every pore more resistant to fouling.
In principle, the rejection force between membrane surface and
particles is proportional to the negative charge density/potential
of the respective extracellular polymeric substances (EPS, poly-
saccharide and proteins) colloids/sludge particles and the nega-
tive charge/potential of the membrane. A 0.05 mV surface may
exert an electric force onto a particle that is 1000 times stronger
than the Brownian (diffusion) force [12]. By applying a negative
potential to a cathode membrane, the repulsion force on the EPS
or sludge foulants can be increased, compared to a membrane
surface which only has a Zeta potential. Using a membrane
cathode in MBR is expected to control fouling effectively. This
idea was studied and tested in this paper.
To make a membrane conductive, researchers coated an ultrathin
gold layer on a polyethersulfone membrane [13]. Huotari et al. [14]
improved ux and permeate quality, by using a carbon ber-carbon

0376-7388/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.memsci.2012.11.066
 L. Liu et al. / Journal of Membrane Science 429 (2013) 252258
1. head tank;
1 2. control tank;
3. DC electrical source;
4. Reactor A with
electric field
3 5. Reactor B without
electric field
2 to the conductive membrane; 0 V/cm, 0.2 V/cm, 0.4 V/cm voltage
4 5
Fig. 1. Scheme of MBR with and without electric eld.
composite as the conductive membrane cathode in ltering oily
wastewater. However, these conductive membrane cathodes are
expensive and complex to make, and difcult to enlarge. A conduct-
ing polymer, polypyrrole (PPy) is cheap, stable and safe, and easily
commercialized. It can be synthesized quickly from pyrrole via
electrochemical or chemical oxidation reactions, and the conductivity
can be maintained in MBR (where polyaniline could not, it had been
tested in our lab). The PPy had been used in sensing/ion exchange
membranes, electrochemical electrode and biomedicine [1519].
A PPy-coated stacked membrane system has been used to separate
lysine and aspartic acids under an electric eld [20] and showed great
potential, but there were few reports about the use of PPy in
preparing conductive and hydrophilic membrane and in controlling
membrane fouling in MBR.
In this study, a terylene lter cloth was chosen as the basement
membrane, and PPy was formed and coated onto the basement
membrane by chemical oxidative polymerization. This made the
membrane conductive and more hydrophilic. An anionic surfactant
dopant, sodium dodecyl benzene sulfonate (SDBS), was used to
neutralize the positive charge of PPy, increase the conductivity and
facilitate the application of an electric eld to inhibit the adsorption of
electronegative, extracellular particles on the membrane surface. The
modied membranes were tested in a MBR to examine their anti-
fouling performance under different electric eld strengths. The
optimal SDBS dosage and voltage drop were determined and then
used in long-term ltration tests (17 days) to examine the stability
and feasibility of these membranes in practical use.
2. Materials and methods
2.1. PPy-modication of polyester lter cloth membrane.
To prepare the composite membrane, we dissolved 15.6 g
FeCl3 6H2O in 1000 mL of water and added 0 g/0.5 g/1.0 g/2.0 g
SDBS to that solution. Two wet pieces of 23 cm  23 cm polyester
lter cloth (nominal pore size 22 mm) were immersed in the
solution, and then 4 mL of pyrrole (used as received) was added to
start the reaction, which took place in an ice water bath and
under magnetic stirring. After 3 h, the membranes were removed,
washed with water, and dried in air.
2.2. Operational conditions and analytical methods.
Two reactors with the same size and structure were used to
conduct parallel tests. The effective volume of a single MBR was
12 L, and the sludge was taken from the Dalian Chunliu
253
Wastewater Treatment Plant. The at sheet membrane module
used in the MBR had an area of 0.0512 m2.
The inuent contained 3 g NH4Cl, 1.5 g KH2PO4, 0.2 g
CaCl2  H2O, 0.9 g FeSO4  7H2O and 30 g sucrose per 90 L tap
water. Two stainless nets were placed 5 cm away from each side
of the membrane to act as the anode. A DC electrical source
(ATTEN, APS3003Si, China) provided the voltage drop in the MBR
drops were used during optimization experiments. SDBS was
used to neutralize the positive charge of PPy; the doping was
optimized with dosages of 0 g, 0.5 g, 1.0 g and 2.0 g.
Gravity ow was adopted as the rapid ltration test, the xed
water head drop (WHD) was 83 cm (transmembrane pressure
(TMP) was 8.14 kPa), and the mixed liquor suspended solids
(MLSS) concentration was 4238 mg/L, the efuent volume was
measured every 5 min and the ux was the average value of that
5 min, total ltration time was 90 min, each ltration was
triplicate. Constant aeration was provided at 0.15 m3/h.
The stability and availability of the membrane was investi-
gated by long-term operation, when peristaltic pumps with a
rotation speed of 16 rpm were used to apply a constant suction
speed to draw efuent out of MBR (Fig. 1). The initial MLSS was
6370 mg/L; these operated for 5 min and then stopped for 1 min.
Constant aeration was provided at 0.15 m3/h.
The total ltration resistances changes, reecting the fouling
difference under this constant suction speed were compared. The
ltration resistances were calculated using the Darcy formula [21].
Also the TMP, the reversible and the irreversible resistances of the
two case comparisons were measured and calculated. The two
comparison cases were: case one, blank membrane without electric
eld and the PPy modied membrane with electric eld; case two,
PPy membrane with or without applied electric eld, respectively.
The pure water ux of the membrane module was measured
using pure water with 83 cm water head drop (WHD), and the
membrane pore diameter was measured with the Bubble Point
Method (China national standard, GB/T 24219-2009). An efuent
sample was taken every ve minutes to calculate the membrane
ux, and the TMP was measured by vacuum meter. Weight
increase due to coated PPy and dopants per membrane area were
measured using six pieces of 2 cm  1 cm membrane cut from
each kind of prepared membrane, and Eq. (1) was used for
calculations, only the average values were reported.
The critical uxes of the blank and modied membrane in
sludge suspension (MLSS of 4.835 70.93 g/L) were determined
using a ux stepping method [22] and 40 cm2 membrane. The
ux was regulated using peristaltic pumps rotating at different
speed (2.5 rpm, 5 rpm, 7.5 rpm and 10 rpm), and the sludge
suspension was stirred using magnetic stirrer at 500 rpm. The
efuent and TMP were recorded for critical ux analysis.
The electric resistance of different membrane was measured
by xing two probes on the two short sides of that 2 cm  1 cm
membrane; the average electric resistance value between the two
long sides (2 cm) was obtained from six measurements.
W c W b
Wi 1
A
Wi: Weight increment of unit membrane area (mg/cm2).
Wc: Average weight of composite membrane (2 cm 
1 cm, mg).
Wb: Average weight of blank membrane (2 cm  1 cm, mg).
A: Area of membrane (2 cm2).
The dynamic contact angle of the membrane was determined
using a dynamic contact angle analyzer (DCA-322, America).
254 L. Liu et al. / Journal of Membrane Science 429 (2013) 252258
The EPS was extracted and determined via modied heating
method [23]. Scanning electron microscope (SEM) (JSM-5600LV,
Japan) was used to show the surface and morphology of the
membranes.
3. Results and discussion
3.1. Properties of the composite membrane.
The PPy coating easily formed on the membrane. The process
blackened the membrane and changed its properties, as shown in
Table 1. The weight increment per unit area, electric resistance,
pore size, dynamic contact angle and water ux of the membrane
were different after PPy coating. The electric resistance of
the composite membrane decreased as the amount conductive
polymer PPy and the coated weight increased. The electric
resistance did not decrease when the amount of SDBS used during
polymerization increased from 1 g/L to 2 g/L. Thus, it was not
necessary to increase the SDBS concentration further.
The pore size of the membrane decreased 63.7% after coating
with PPy, but which value was reduced to 49.4% upon doping by
0.5 g/L SDBS. PPy reduced the membrane pore size, for it poly-
merized around the membrane pores and narrowed them. A
reasonable amount of surfactant SDBS could maintain the pore
size by well dispersing pyrrole [24], so PPy took less space in the
pore. The pore size reduced accordingly with the weight incre-
ment after the SDBS was doped. The anionic surfactant SDBS has a
Critical Micelle Concentration (CMC) of (1.370.5)  10  3
mol/dm3 at 30 1C [24]. When the concentration of the surfactant
was less or slightly higher than the CMC (from 0.5 g/L to 1.0 g/L),
oily pyrrole would be dispersed and deposited on the membrane
very well, so the weight increment per unit area increased (from
4.18 mg/cm2 to 7.96 mg/cm2). Oppositely, when the concentra-
tion of SDBS was too high above the CMC, there would be a large
number of SDBS micelles in FeCl3  6H2O solution, their hydro-
philic groups on micelle surface would face water and those
hydrophobic groups just aggregate inside, then the oily pyrrole
was included in the SDBS micelles and not polymerized on
membrane tightly, that decreased the weight increment.
The morphology of the modied membranes was shown in
Fig. 2. The PPy was coated on the ber surface after modication.
The amount of PPy on the membrane ber surface increased
when SDBS concentration was increased from 0.5 g/L to 1 g/L. And
there was lamellar structure on those ber surface (Fig. 2bd), as
mentioned above, the pyrrole would disperse and deposit well.
But the PPy amount on ber surface was decreased when SDBS
concentration was further increased to 2 g/L (Fig. 2e), since a large
ratio of PPy particles may be embedded in SDBS micelles and less
of them could be polymerized on ber surface. The morphology
changes in SEM images agree with the trend of weight increase
after modication.
Table 1
Parameters of membranes before and after modication with PPy/SDBS.
Membrane modication Weight increase Resistance
(mg/cm2) (kO/cm)
Blank 0 N
0 g/L SDBS/3.868 g/L PPy 2.91 7 0.13 4.13 7 3.16
0.5 g/L SDBS/3.868 g/L PPy 4.18 7 0.18 3.12 7 2.93
1.0 g/L SDBS/3.868 g/L PPy 7.96 7 0.31 1.84 7 0.98
2.0 g/L SDBS/3.868 g/L PPy 5.08 7 .06 2.11 7 1.4
F-Flux of modied membrane; F0-original ux of blank membrane. D average pore diameter of modied membrane; D0-average pore diameter of blank membrane. The
TMP was 8.14 kPa.
The dynamic contact angle of the modied membranes stea-
dily decreased as coated PPy and doped SDBS increased up to a
SDBS concentration of 1.0 g/L. Accordingly, these modications
increased the hydrophilicity of the membrane dramatically. The
coated PPy increased the hydrophilicity of the membrane, the
SDBS, also hydrophilic, decreased the dynamic contact angle from
51.771 to 22.611, then to 01; This result was different from that of
Ref. [25], which found that the hydrophilicity of PPy polymerized
by electrochemical oxidation was lowest when the concentration
of SDBS was 1.2 mmol/L (CMC). This inconsistency in results
might be caused by the state of the surface, or the difference
between in using electrochemical and chemical polymerization
methods. The rough PPy was polymerized via chemical approach
(Fig. 2), but the structure of PPy lm from electrochemical
oxidation with 1.2 mmol/L SDBS was most compact and homo-
geneous [25], and previous study also indicated that roughness
reduced the contact angle [26].
The water ux of the membrane decreased slightly when PPy
covered/narrowed the pores. But the water uxes were almost the
same with that of blank membrane as the SDBS dosage increased
(from 0.5 to 1.0 then 2.0 g/L) during polymerization. This can be
attributed to the increase in the hydrophilicity of the membrane
and the reduction of contact angle of the membranes from blank
51.81 to the modied 22171(SDBS 00.5 g/L) and then to 01
(when SDBS concentration was 1.0 or 2.0 g/L).
The ux-TMP proles in Fig. 3 indicated that the TMP increased
signicantly when the membrane ux reached 200 L/m2/h, for both
the blank membrane and modied membrane under the set
experimental conditions, and no apparent TMP increase had been
observed when the ux was 75 L/m2/h, so the critical ux of those
membranes should not be higher than that value. There was no
obvious difference in critical ux between all of those membranes.
3.2. Optimization of SDBS doping and voltage drop
The ux measurement was used to evaluate the anti-fouling
capacity of the membrane. Different PPy composite membranes
doped by different amounts of SDBS all maintained ux better than
without SDBS (Fig. 4). Comparing to the blank membrane, the ux (at
constant TMP) was increased to 2.4, 3.4, 5.5 and 5-fold when the
amount of dopant during polymerization was raised from blank
membrane to PPy modied membrane, 0 g/L to 0.5 g/L, 0.5 g/L to
1.0 g/L, and 1.0 g/L to 2.0 g/L, respectively, at the end of the rst cycle.
This behavior is related to membrane pore size and hydrophilicity, for
previous studies showed that membrane contamination can block
bigger pores then lead to greater ux decline, and hydrophilic
membrane was less prone to fouling [27,28], and the blank mem-
brane had the biggest pore size and worst hydrophilicity, the
hydrophobic foulant could be adsorbed on the membrane surface
and aggregated in the membrane pore easily.
The increase in ux slowed when the concentration of SDBS
was higher than 1.0 g/L, so there was no need to increase the
Pore size reduction Dynamic contact angle Water ux Flux reduction
(1-D/D0) (%) (advancing) (1) (L/h/m2) F/Fo
0 51.77 488.1 1
63.7 22.61 483.4 0.99
49.4 17.76 484.8 0.99
73.8 0 488.0 1
67.3 0 490.8 1.01
 L. Liu et al. / Journal of Membrane Science 429 (2013) 252258 255

Fig. 2. The SEM photos of blank membrane (a), PPy modied membrane (b), PPy modied membrane with 0.5 g/L SDBS (c), with 1 g/L SDBS (d), with 2 g/L SDBS (e) and the
photo of membrane before and after modication with PPy (f).

300 0.05 SDBS content further. The ux of 1.0 g/L SDBS modied mem-
Blank brane was higher than that of 2.0 g/L in the rst cycle, but it was
250 PPy reversed in the second and third cycles. There are two reasons for
0.04
0.5 g SDBS that phenomenon, the rst one, the pore size of 2.0 g/L SDBS one
200
1 g SDBS was more than that of 1.0 g/L SDBS one, the ux could be
Flux (Lm-2h-1)

TMP (MPa)

2 g SDBS 0.03 recovered more easily after ltration; the second one, more PPy
was polymerized on the surface of membrane but not in the pore
150
when 2.0 g/L SDBS was added (this phenomenon could be
0.02 observed during the polymerization process), which could
100
work as dynamic membrane and maintain ux recover [29,30].
The dosage of 2 g/L was chosen for the long-term ltration
0.01
50 experiment.
As the voltage drop was the key parameter in controlling
0 0.00 membrane fouling by the electric eld, it needed optimization.
0 15 30 45 60 The result (Fig. 5) showed that for the same membrane, without
Time (min) electric eld the ux dropped quickly/sharply under constant
TMP, the ux was 83% and 79% for those membranes operating
Fig. 3. Flux-TMP proles for blank and modied membrane. MLSS: 4.835 7 0.93 g/
under 0.2 and 0.4 V/cm voltage drop at the end of the rst cycle,
L , membrane area 40 cm2, stirring speed of magnetic stirrer: 500 rpm.
respectively. The results indicated that the bigger voltage drop
was good for maintaining stable ux during the rst two cycles;
0.2 V/cm voltage drop produced the highest ux in the third cycle.
600 Blank membrane PPy This was good for saving energy. The higher voltage drop
PPy with 0.5 g SDBS PPy with 1 g SDBS provided bigger repulsive force to membrane foulant, so there
PPy with 2 g SDBS was better permeation property during the rst two cycles. But it
500 might reduce the positive effect of the dynamic layer in main-
taining stable ux.
Reasonable amount dynamic cake layer on large pore mem-
Flux(L h-1 m-2)

400
brane could delay pore blocking and membrane fouling, for the
cake layer could protect membrane surfaces and its pores from
300
being fouled, as EPS, other soluble organics and colloidal particles
were resisted or degraded by that layer [29,30]. The membrane
200 pore would be blocked directly without the protection of that
dynamic layer (0.4 V/cm), the ux could not be recovered as much
100 as that one with the layer (0.2 V/cm). Thus, it was not strange that
a 0.2 V/cm voltage drop could ultimately produce the biggest ux
in the third cycle. This voltage drop value was chosen as a
0
subsequent experimental parameter.
0 50 100 150 200 250
The higher voltage drop also will produce side effects and
Time (min)
reactions such as formation of H2 and O2, and causing pH change
Fig. 4. The permeate ux changes for the blank membrane and PPy modied in the close-by area of an electrode. As the sludge particles, EPS
membrane in MBR (TMP 8.14 kPa, MLSS 4238 mg/L). and colloids all contain water and ions in their electric double
256 L. Liu et al. / Journal of Membrane Science 429 (2013) 252258

500 membrane (bigger pore size) without electric eld, but the
efuent of the blank membrane was less than that of PPy
modied membrane at the later stage, due to serious membrane
fouling (Fig. S1a). The irreversible resistance of modied mem-
450
brane with applied electric eld was 1/2 that of the blank
membrane at the end of the test (Table 2).
Flux(L h-1 m-2)

The lter cake on one side of the membrane (0.0256 m2) after
400
long-term ltration was diluted to 600 mL, and parameters such
as MLSS, MLVSS, sludge diameter and EPS were measured to
determine the differences between the test group and control
group. The results were shown in Table 3.
350 The MLSS and EPS values from the blank membrane were
Without electric field approximately 3-fold and 2-fold those of the composite mem-
0.2 V/cm brane, respectively (no signicant difference between the two
0.4 V/cm bulk phase sludge), which explained the lower TR and TMP in
300 MBR with composite membrane. This illustrates the effect of the
0 50 100 150 200 250
electric eld in directly pushing sludge away from the membrane
Time (min) surface, making the lter cake layer loose (be easily cleaned by
scouring) or enhancing the back-diffusion of the sludge/colloids
Fig. 5. The permeate ux of modied membrane under different voltage drop in
MBR (TMP 8.14 kPa, MLSS 4238 mg/L). by the electrophoresis/Coulomb force(within close distance to the
membrane).
The MLVSS/MLSS ratio for the blank membrane was close to
2.5 that of bulk phase sludge, but the value of the lter cake from the
test group was less, which might be caused by inorganic ions such
as Ca2 and Mg2 , attracted by the negative charges.
2.0 The EPS in the sludge of the test group (55.52 mg/g MLVSS)
0.2V/cm, 2g SDBS, PPy mem. was slightly less than that in the control group (68.82 mg/g
Total resistance (1013 m-1)

Blank membrane
1.5
1.0
0.5
0.0
0 6
Time (day)
Fig. 6. The total resistance of the modied membrane in a long-term test (blank
membrane, without electric eld VS PPy modied membrane with 2 g/L SDBS under
0.2 V/cm voltage drop. Initial MLSS6370 mg/L, rotate speed of pump 16 rpm).
layer, higher electric eld may cause redistribution of surface
charges, or generate an inverse internal electric eld to reduce the
effect of external electric eld [12].
3.3. Long-term ltration test.
Long-term ltration (17 days) was carried out to examine the
stability and availability of the membrane. The lter cloth has
higher intrinsic permeate ux, it and the PPy/SDBS modied
membrane both could steadily operate at a ux 24 L/m2/h
when MLSS was  6 g/L in MBR.
There were difference in changes of the total membrane
resistance (TR) (shown in Fig. 6) between the blank membrane
and the PPy modied membrane, initially the TR of PPy modied
membrane was higher than the blank, because of smaller pores.
But, later it was smaller than the blank, due to the effect of the
electric eld and the more hydrophilic membrane property. The
cumulative efuent volume and TMP were shown in Fig. S1a and
S2a (Supporting information), respectively. The cumulated total
permeate volume was similar for the composite membrane doped
by 2 g/L SDBS under a 0.2 V/cm voltage drop and the blank
MLVSS). For the test group, the EPS in lter cake (54.62 mg) of
the test group was about half that of the control group
(118.52 mg). This occurred because the electric eld pushed the
sludge as well as proteins and polysaccharides (EPS) away
effectively, so less hydrophobic EPS was adsorbed in the hydro-
philic membrane surface, thus both the reversible fouling by cake
layer and the irreversible fouling by the gel layer was reduced. It
is reported EPS may be degraded by microorganisms in the
stressful cake layer condition, where normal uptake and metabo-
lism in microbes may be affected. With electric eld, in the
thinner cake layer, the condition (such as dissolved oxygen
12 18
concentration) is not as stressful as that in the thick cake layer.
Results from comparison tests with or without applying
electric eld (0.2 V/cm) using PPy/SDBS (2 g/L) modied mem-
brane in two MBR, operated in parallel, were presented
(Table 2 and 4, and Fig. 7). Applying the electric eld, a dramatic
reduction (nearly 67%) in ltration resistance was achieved
during the 16 days operation test. Also the electric eld reduced
the deposited sludge in cake layer by 22%, as shown in Table 4.
After the test and physical cleaning of the membranes, the
measured irreversible resistance of modied membrane without
applying electric eld was  5 times that of the modied
membrane with applied electric eld (0.2 V/cm) (Table 2).
General efuent turbidity was o1NTU.
The forces exerted on a particle of sludge or EPS colloid in
electric eld was showed in Fig. S3. The effect of operating electric
eld in fouling reduction can be explained by the two exerted
forces on a charged particle (EPS or sludge) from the electric eld.
The electric eld force and the Coulomb force (electrostatic force)
within close distance to the membrane are times bigger than the
Brownian back diffusion force [12], depending on the particle size
and charge density. The electric eld force can be calculated by
Fe Eq, where E is the electric eld strength and q is the charge of
the particle; The Coulomb force is generated by two charge
particles/bodies and calculated by Fc kq1q2/r2, where k is con-
stant, q1 and q2 are the charges of two particles or bodies, r is the
distance of those two particles or bodies. For the same sludge/EPS,
when the electric eld is applied in MBR, its Coulomb force with
cathode membrane will be increased for the charges/potentials of
 L. Liu et al. / Journal of Membrane Science 429 (2013) 252258 257

Table 2
The membrane resistances after long term experiment.

Blank membrane1 PPy membrane with electric1 Ratio of resistances (Without/with electric eld)

Total resistance (1013 m  1) 2.4 0.79 3.04

Reversible resistance (1013 m  1) 2.327 0.757 3.07
Irreversible resistance (1013 m  1) 0.073 0.033 2.21
PPy membrane2 PPy membrane with electric2 Ratio of resistances (Without/with electric eld)
Total resistance (1013 m  1) 1.15 0.37 3.11
Reversible resistance (1013 m  1) 1.069 0.354 3.02
Irreversible resistance (1013 m  1) 0.081 0.016 5.06

The superscript 1 means the rst long term test (blank membrane, without electric eld VS PPy modied membrane with 2 g/L SDBS under 0.2 V/cm voltage drop) and the
superscript 2 means the second long term test (PPy modied membrane with 2 g/L SDBS VS PPy modied membrane with 2 g/L SDBS under 0.2 V/cm voltage drop).

Table 3
The parameters of sludge and lter cake in test group (TG, PPy/SDBS modied membrane with 0.2 V/cm electric eld) and control group
(CG, blank membrane).

MLSS (mg/L) MLVSS (mg/L) MLVSS/MLSS Sludge diameter (mm) EPS EPS in lter cake (mg)
(mg/gMLVSS)

Initial sludge 6370 5318 0.835 749.17 23.30 N/A

Final sludge of TG 8776 7484 0.853 N/A 55.52 N/A
Final sludge of CG 7828 6676 0.853 N/A 68.82 N/A
Filter cake of TG 1952 1544 0.791 N/A 58.96 54.62
Filter cake of CG 5840 5048 0.864 N/A 39.13 118.52

The sludge from the lter cake had been diluted to 600 mL. TG, test group, PPy modied membrane with 0.2 V/cm electric eld. CG, control
group, Blank lter cloth membrane, without electric eld.

1.2 forces will be reduced due to reduction of the charge on particles,

though the lterability of the sludge could be enhanced [8].
1.0
Furthermore, it will be useful to know the stability of the
PPy membrane with electric field PPy-doped membrane; more tests to check membrane stabilities are
Total resistance (1013 m-1)

PPy membrane without electric field
0.8
0.6
0.4
0.2
0.0
0 2 4 6 8 10
Time (day)
Fig. 7. The total resistance of the modied membrane in a long-term test (PPy
modied membrane with 2 g/L SDBS VS PPy modied membrane with 2 g/L
SDBS under 0.2 V/cm voltage drop. Initial MLSS 5174 mg/L, rotate speed of
pump 16 rpm).
membrane have been increased, as the cathode is under electric
eld. Those forces could enhance the back-diffusion of membrane
foulants and inhibit the compression of lter cake layer, which
positively contribute to membrane fouling reduction. When the
membrane surface is covered by a cake layer, which acts like a
conductive layer too, the Coulomb force between the particles
and membrane may be reduced, if the lter cake layer has less
negative charge/smaller potential.
If there is electro-coagulation (anode releases Fe3 or Al3 as
coagulant), the negative charge of the particles will be neutralized,
then the electrostatic double layer will be compressed, those two
ongoing. It is proved that PPy can be in-situ formed in the normal
casting solution for preparing at membrane and be integrated in
the spinning process for hollow ber production, which indicates a
feasible application of electric eld in practical fouling reduction. It
may reduce the chemical cleaning frequency, while increase the ux
recovery ratio after physical cleaning. This is helpful for practical
application of MBR in wastewater treatment for fouling reduction
and treatment efciency enhancement.
4. Conclusion
Alone or with doped SDBS, PPy modication of the lter mem-
12 14 16
brane increases the membrane electrical conductivity, reduces the
pore size, contact angle and membrane fouling. Fouling was further
greatly reduced at very low cost by applying a minute electric eld
(0.2 V/cm) to the PPy/SDBS modied membrane (as cathode), as the
very negative potential on the modied membrane expels EPS and
sludge, and helps maintaining a higher permeate ux.
Applying a 0.2 V/cm voltage drop to the (2 g/L) SDBS/PPy
modied membrane, the total ltration resistance was  1/3
and the irreversible resistance was 1/2.2 that of the blank
membrane on the last day and its irreversible membrane resis-
tance was 1/5 that of the (2 g/L) SDBS/PPy membrane without
electric eld, in long term MBR tests.
Acknowledgement
The authors appreciate the nancial support from China
natural science funding (No. 21177018) and the Brook Byer
Institute for Sustainable Systems.
258 L. Liu et al. / Journal of Membrane Science 429 (2013) 252258

Table 4
The parameters of sludge and lter cake in test group (TG, PPy/SDBS modied membrane with 0.2 V/cm electric eld) and control group (CG, PPy/SDBS
modied membrane without electric eld).

MLSS (mg/L) MLVSS (mg/L) MLVSS/MLSS Sludge diameter (mm) EPS EPS in lter cake (mg)
(mg/gMLVSS)

Initial sludge 5174 3618 0.699 293.40 58.45 N/A

Final sludge of TG 6850 5044 0.736 N/A 34.28 N/A
Final sludge of CG 6880 5116 0.744 N/A 36.19 N/A
Filter cake of TG 2180 1544 0.708 N/A 54.90 50.86
Filter cake of CG 2812 1966 0.699 N/A 57.93 68.33

The sludge from the lter cake was diluted to 600 mL.

Appendix A. Supporting information
Supplementary data associated with this article can be found
in the online version at http://dx.doi.org/10.1016/j.memsci.2012.
11.066.
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