Ionics (2010) 16:75–80
DOI 10.1007/s11581-009-0372-y
ORIGINAL PAPER
Investigation of filtration capability of conductive composite
membrane in separation of protein from water
Sayed S. Madaeni & S. Molaeipour
Received: 1 October 2008 / Revised: 21 April 2009 / Accepted: 28 July 2009 / Published online: 12 August 2009
# Springer-Verlag 2009
Abstract In this study, composite membrane was prepared
by chemical polymerization of pyrrole on the surface of the
ultrafiltration membrane using ferric ions. The performance
of the prepared membrane was characterized by filtration of
bovine serum albumin (BSA) solution through the mem-
brane in various conditions. For conductive membrane,
higher rejection was obtained compared with non-
conductive membrane. This effect can be attributed to the
conductivity of the membrane. The negatively charged
membrane surface acts as a barrier against BSA. Moreover,
the protein is pushed back due to the electrostatic effect.
This results in higher rejection. For conductive membrane,
lower fluxes were obtained for the same condition. It can be
attributed to the partial blocking of the membrane pores
with polypyrrole. The pH effects were complex. Around
isoelectric point, the protein particles lose their charge and
produce larger particles, which settle on the membrane
surface resulting in lower flux and higher rejection. At the
pHs far from the isoelectric point, rejection was decreased.
Keywords Membrane . Ultrafiltration . Conducting
polymers . Separation . BSA . Chemical diffusion .
Polymer electrolytes . DC conductivities
Introduction
Apart from their electronic properties, conducting poly-
mers have also spread their wings in membrane-based
S. S. Madaeni (*) : S. Molaeipour
Membrane Research Center, Chemical Engineering Department,
Razi University,
Kermanshah, Iran
e-mail: smadaeni@yahoo.com
separation science. Membrane processes are receiving
attention of the scientific community as they are clean
and of low energy consumption. Actually, due to the
random distribution of fibrils of conducting polymers
without any orientation or alignment [1], their use in the
separation area is restricted. Only few reports are available
in gas separation and pervaporation [2–4]. The conducting
polymers have also shown their potential regarding
selective ion transport in the electrical field. The electron
injection/ejection through the dopants (by redox reaction)
imparts the charge transport property in the electrical field.
The dopant counter ion is closely bound to the polymer’s
ionic repeat unit sites by electrostatic forces, which serves
overall charge neutrality of the system. Poor mechanical
strength of the conducting polymers restricts their appli-
cations in various areas as well as in membrane area.
Preparation of composites is one of the ways to increase
their applicability [5–7].
Many polymers have been employed for preparation of
conductive membranes including poly(vinylidene fluoride)/
polyaniline blends [8], sulfonated polyphenylsulfone [9],
sulfonated poly(ether ether ketones) [10] and a mixture of
polycarbonate-polypyrrole [11]. Specific procedures have
been used for modification of non-conductive membrane to
prepare conductive membranes. The techniques include
irradiation treatment of polyvinylfluoride films [12], direct
sulfonation of poly (vinyl fluoride) [13] and controlled
sulfonation of EPDM [14].
Among conducting polymers, polypyrrole is one of the
most promising materials for multifunctionalized applica-
tions due to its good environmental stability and higher
conductivity compared with other conducting polymers
[15]. Polypyrrole has a tight, rigid structure with weakly
basic anion-exchangeable groups, which is easily polymer-
ized by chemical or electrochemical oxidation.
76
The polymerization of pyrrole within polymeric mem-
branes produces composites with desirable properties.
Pyrrole has been polymerized within cation-exchange
membranes to produce membranes with electrochemically
controlled ion-exchange characteristics [16]. For example,
the combination of the electroactivity of polypyrrole and
ion-exchange capacity of Nafion provides materials with
novel properties [17]. The selectivity of ions through
polypyrrole/porous polypropylene composite membrane
can be highly controlled by potential application [18].
In this study, composite membrane was prepared by
chemical polymerization of pyrrole on the surface of the
ultrafiltration membrane using ferric ions. Chemical poly-
merization of pyrrole on polysulfone membrane appears to
be a general and more useful technique for the preparation
of composite membranes. The performance of the prepared
membrane was evaluated. The passage of charged mole-
cules (bovine serum albumin (BSA)) through original and
modified membranes were compared with finding the effect
of conductivity on permeate flux and rejection of BSA.
Experimental
Chemicals
Pyrrole, ferric chloride, NaH2PO4, and Na2HPO4, all from
Merck, and crystalline BSA (A-2934, Lot93H0291) from
Sigma were used in the experiments. BSA is an oblate
ellipsoid-charged protein with dimensions of 14×4 nm and
the molecular weight of 67,000 D. Freshly distilled pyrrole
was employed for each trail.
Amicon PM30 (MWCO=30 kDa) membrane was used
as support. The details of the membrane are presented in
Table 1. Membrane was prepared for use according to the
information provided by the manufacture.
Apparatus
All experiments were carried out in a 110-ml capacity batch
dead-end cell with a membrane area of 15.2 cm2. The cell
Table 1 Characteristic of PM30 membrane
Manufacturer Amicon
Material Polysulphone
Hydrophobicity Hydrophobic
MW cut-off (kDa) 30
Water fluxa (l m−2 h−1) 640–1130
Permeability (109 m Pa−1 s−1) 1.7–3.1
Membrane resistance (1011 m−1) 3.5–4.0
a
ΔP=100 kPa
Ionics (2010) 16:75–80
consisted of a cylindrical vessel containing the test solution;
two circular end pieces were made from Perspex and a
porous medium to support the membrane. The top end
piece of the cell contained a feed and a gas inlet and a
pressure relief valve. Stirring was achieved by an internal
magnetic bar (25.4 mm long and 6.4 mm diameter)
suspended 2 mm above the membrane. Nitrogen gas was
used to pressurize the cell to the operating pressures. A
reservoir was connected to the cell to replenish the
permeate (Fig. 1).
Preparation of conductive membrane
In this study, the conductive membrane was prepared with
formation of a thin layer of polypyrrole on the surface of
the support (PM30 ultrafilter).
The support was firstly soaked in a mixture of distilled
water and ethanol (50% each) for 30 min. Then it was left
in 25 ml pyrrole solution (0.2 M) for 60 min. After that, the
membrane was taken out and immersed in 25 ml ferric
chloride solution (0.2 M) without drying. When the support
was soaked in oxidant medium, chemical polymerization at
the interface results in formation of a thin layer on the
surface of support. Polypyrrole film completely covered the
support. The appearance of black color on the support
indicated the formation of polypyrrole. The thickness of
polypyrrole depends on the polymerization time. After
60 min, the membrane was taken out from FeCl3 solution
and then washed with water to remove the excess monomer
and the adhered oxidizing agent. As the final stage, the
membrane was dried by placing between two sheets of filter
paper [1].
Conductivity measurement
To confirm the polymerization of pyrrole in the mem-
brane matrix, the electrical conductivities of the prepared
membranes were measured. The prepared membranes
were set on a completely non-conducting surface. Two
metal elements were placed at the ends of the membrane.
The distance between the two elements was 1 cm. The
surface resistivity of the membrane was measured using
an ohm meter (Escort EDM-169 S, Taiwan) connected to
the metal elements [19]. The average measured resistance
was 10 KΩ. It appears that the conductivities of the
composite membranes are in the insulating range.
Filtration procedure
The performances of the prepared membranes were
characterized by filtration of BSA solution through the
membrane. All experiments were carried out in a batch cell.
The experiments were started after a 100 ml of BSA
Ionics (2010) 16:75–80 77

Fig. 1 Schematic of dead end

cell

solution was poured into the cell which was quickly
pressurized by nitrogen gas. The feed solution was fed
continuously from a feed reservoir connected to the cell to
replenish the permeate. The experiments were carried out at
ambient temperature (24±1°C) and operating pressure of
100 kPa. The membranes were tested during 105 min. The
system was run for 30 min to reach to steady state. After
that, the permeate was collected every 15 min and weighed
for calculating the flux under 100 kPa transmembrane
pressure.
The magnetic stirrer was started with a stirring speed of
400 rpm prior to the filtration. The concentration of feed
was 0.15 g/l of BSA at neutral pH.
The flux (F) was measured gravimetrically with a
Mettler PJ 6000 electronic balance by continuously
weighing the permeate. The retention of BSA was
determined as:
R% ¼ 100½1
ðCp=Cf Þ
Where Cp and Cf are BSA concentrations in permeate
and feed, respectively.
Determination of BSA concentration
The retention of protein was investigated by measuring the
BSA in the permeate. The absorption of each sample was
measured at 280 nm using spectrophotometer (JASCO,
FP6200). Each measurement was carried out three times
and the average number was reported to reduce the
experimental error.
Results and discussion
Effect of time
The effect of time on BSA rejection using conductive and
non-conductive membranes is depicted in Fig. 2. The
rejection was increased during the test. This behavior is
expected due to accumulation of the BSA particles on the
surface of the membrane or within the membrane matrix.
For conductive membrane, higher rejection was obtained
compared to non-conductive membrane. This effect can be

100 160

95
140
90
120
Flux (Kg/m2.h)
Rejction (%)

85
100
80
80
75
60
70

65 40

60 20
0 20 40 60 80 0 20 40 60 80
Time (min) Time (min)
non-conductive conductive non-conductive conductive

Fig. 2 Rejection versus time for BSA solution using conductive and Fig. 3 Flux versus time for BSA solution using conductive and non-
non-conductive membranes (one bar, 24°C, 0.15 g/l, 400 rpm) conductive membrane (one bar, 24°C, 0.15 g/l, 400 rpm)
78 Ionics (2010) 16:75–80

90 100

80 90
Rejection (%)

Rejection (%)
70 80

60
70
0 1 2 3 4
0 0.05 0.1 0.15 0.2
Pressure (bar) Concentration (g/lit)
non-conductive conductive
non-conductive conductive
Fig. 4 Influence of transmembrane pressure on BSA rejection using
Fig. 6 Influence of feed concentration on BSA rejection using non-
non-conductive and conductive membranes (24°C, 0.15 g/l, 400 rpm)
conductive and conductive membranes (one bar, 24°C, 400 rpm)

attributed to the conductivity of the membrane. BSA has
negative charge in neutral pH. The negatively charged
membrane surface acts as a barrier against BSA passage
through the membrane. A part of the protein is pushed back
due to the electrostatic effect. This results in higher
rejection.
The effect of time on water flux using conductive and non-
conductive membranes is depicted in Fig. 3. Flux is declined
during the test. This is a typical behavior for ultrafiltration
which is due to the concentration polarization and fouling.
Fouling significantly blocks the membrane pores. This
provides a resistant against passage through the membrane.
For conductive membrane, lower fluxes were obtained for
the same condition. This can be attributed to the partial
blocking of the membrane pores with polypyrrole.
Effect of transmembrane pressure
The influence of transmembrane pressure on BSA rejection
and permeate flux were studied. The results in Figs. 4 and 5
indicate that pressure increment causes a decline in rejection
of BSA particles and an improvement in water flux for both
non-conductive and conductive membranes. Lower retention
at higher ΔP is typical in UF and can be explained by a
higher concentration at the membrane surface due to
increased polarization giving higher passage of the species.
Effect of feed concentration
The effect of feed concentration on BSA rejection and
water flux is presented in Figs. 6 and 7, respectively. As the

120 140

120
100

100
Flux (Kg/m2.h)

80
Flux (Kg/m2.h)

80
60
60

40
40

20 20

0 0
0 1 2 3 4 0 0.05 0.1 0.15 0.2
Pressure (bar) Concentration (g/lit)
non-conductive conductive non-conductive conductive

Fig. 5 Influence of transmembrane pressure on water flux using non- Fig. 7 Influence of feed concentration on flux using non-conductive
conductive and conductive membranes (24°C, 0.15 g/l, 400 rpm) and conductive membranes (one bar, 24°C, 400 rpm)
Ionics (2010) 16:75–80 79

100 100

90
90
Rejection (%)

Rejection (%)
80

80
70

70
60

60 50
0 200 400 600 800 0 2 4 6 8 10

Stirring speed (rpm) pH

non-conductive
non-conductive conductive

Fig. 8 Influence of stirring speed on BSA rejection using non- Fig. 10 BSA rejection versus pH using non-conductive membrane
conductive and conductive membranes (one bar, 24°C, 0.15 g/l) (one bar, 24°C, 0.15 g/l, 400 rpm)

protein concentration was decreased, BSA rejection was
increased. This phenomenon can be described by higher
concentration at the membrane surface due to increased
polarization giving higher concentration in the permeate.
The results indicate that by increasing BSA concentration,
water flux is decreased. This is due to the formation of a
thicker protein layer on the membrane surface in high
concentration. The 0.15 g/l concentration was selected for
the remaining experiments due to detection limitations at
lower concentrations.
Effect of stirring speed
The effect of stirring speed on BSA rejection and water flux
is depicted in Figs. 8 and 9, respectively. The results
120
105
indicate that higher stirring speed (600 rpm) increases both
BSA rejection and water flux. This phenomenon can be
explained by concentration polarization. At low stirring
speeds, concentration polarization is increased at the
vicinity of the membrane surface. This results in higher
passage of BSA through the membrane and establishment
of higher resistance against flow.
Effect of pH
The pH experiments were performed in a range of 2 to
8. The charge of BSA is the most vital parameter
influencing the filtration behavior. Apparently the BSA
charge depends on the applied pH. At low pHs (e.g., 2)
BSA obtain positive charge. Around isoelectric point
(pH 5.5), BSA particles lose their charge. At higher pHs
100

90
Flux (Kg/m2.h)

90
75
Flux (Kg/m2.h)

60
80
45

30
70
15

0
60
0 200 400 600 800
0 2 4 6 8 10
Stirring speed (rpm) pH
non-conductive conductive non-conductive

Fig. 9 Influence of stirring speed on water flux using non-conductive Fig. 11 Water flux versus pH using non-conductive membrane (one
and conductive membranes (one bar, 24°C, 0.15 g/l) bar, 24°C, 0.15 g/l, 400 rpm)
80
(e.g., 8) BSA exhibit negative charge. In other words, we
covered all possible states of charge (positive, negative, and
neutral) for BSA by manipulating the applied pH.
In order to adjust pH, phosphate buffer was used. Prior
to the main experiments, the membranes were tested with
buffer solution without BSA. The filtration behavior was
similar to distilled water, i.e., buffer’s ions easily pass
through the UF membrane. The passage of small ions
through the ultrafiltration membrane is anticipated. In
summary, BSA rejection is not influenced by the buffer
concentration or composition.
The pH effects on BSA rejection and water flux were
complex. These effects are shown in Figs. 10 and 11,
respectively. The trend for flux variation is a typical
behavior. Around isoelectric point, the proteins lose their
charge and produce larger particles, which settle on the
membrane surface resulting in lower flux. In the pHs far
from the isoelectric point, the particles are dispersed in the
bulk media. Figure 10 indicates that around isoelectric
point, rejection is increased and in the pHs far from the
isoelectric point, this is decreased.
For conductive membranes, the pH effects were inter-
esting. At pH=2, no rejection and at pH=8, no permeate
were observed. BSA has positive charge in pH=2, so it is
attracted by negatively charged membrane surface. This
results in higher concentration polarization in the vicinity of
the membrane leading to higher passage through the
membrane.
BSA is negatively charged at pH = 8 and in this
condition, the negatively charged membrane acts as a
barrier against passage of protein. This results in an
increase in BSA rejection. The barrier was so strong that
no permeation was observed under the applied pressure.
Conclusion
A commercial non-conductive ultrafiltration membrane was
converted to conductive composite membrane using pyrrole
and ferric ions. The filtration of charged species such as
BSA depends on the conductivity of the membrane. Higher
rejections were obtained for conductive membranes com-
pared with non-conductive membrane in the same condi-
tion. The electrostatic partial repulsion of BSA from the
membrane surface or membrane matrix is responsible for
this behavior
The pH effects were complex. Around isoelectric
point, the protein particles lose their charge and produce
larger particles, which settle on the membrane surface
resulting in lower flux and higher rejection. At the pHs
far from the isoelectric point, rejection was decreased.
For conductive membranes, no permeate at pH=8 and no
rejection at pH=2 was observed.
Ionics (2010) 16:75–80
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