Separation and Purication Technology 74 (2010) 230235

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Separation and Purication Technology
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Fabrication of cellulose acetatezirconia hybrid membranes for ultraltration
applications: Performance, structure and fouling analysis
G. Arthanareeswaran
a,
, P. Thanikaivelan
b
a
Membrane Research Laboratory, Department of Chemical Engineering, National Institute of Technology, Tiruchirappalli 620015, India
b
Centre for Leather Apparel & Accessories Development, Central Leather Research Institute (Council for Scientic & Industrial Research), Adyar, Chennai 600020, India
a r t i c l e i n f o
Article history:
Received 14 December 2009
Received in revised form 10 June 2010
Accepted 10 June 2010
Keywords:
Organo-mineral membranes
Mechanical stability
Membrane morphology
Protein separation
Fouling-resistant
a b s t r a c t
Organicinorganic hybrid membranes were fabricated by solution casting using different ratios of
cellulose acetate (CA) and zirconia (ZrO
2
) in N,N

-dimethylformamide (DMF). The addition of ZrO

2
microparticles in the CA matrix was varied from 0 to 7wt.%. The developed membranes were char-
acterized for ultraltration (UF) performance, mechanical stability, morphology and fouling-resistant
ability. It is found that the pure water ux increases from15.6 to 46.7lm
2
h
1
while the tensile strength
decreases from 2 to 1.4N/mm
2
with addition of zirconia from 0 to 7wt.% to pure CA, respectively. Mor-
phological studies indicate that the CA:ZrO
2
hybrid membranes possess asymmetric structure with ultra
scale pores. From the pore statistics analysis, it was seen that the CA:ZrO
2
(6:4 ratio) hybrid membranes
have an average pore radius of 47.52 compared to 26.88 of pure CA membrane. It was found that the
hybrid CA:ZrO
2
membranes exhibit higher permeate ux for the separation of different molecular weight
proteins compared to pure CA membrane. It has been demonstrated that the fouling-resistant ability and
the recycling property of CA:ZrO
2
hybrid membranes are enhanced due to the high ux recovery ratio
with the addition of ZrO
2
in the casting solution.
2010 Elsevier B.V. All rights reserved.
1. Introduction
In recent years, various methods have been developed
to improve the performance of polymeric membranes. Most
researchers have reported the improvements in permeability and
hydrophilic property of polymeric membranes by blending with
polymers or organic modiers usingphase-inversionmethod[13].
Among these, doping of organic additives to polymer to formultra-
ltration membranes is intensively studied. Current membrane
based processes require membrane materials with good thermal
and mechanical stability together with good solvent resistance and
hydrophilicity. Hence, the incorporation of inorganic particles into
the organic polymeric matrices has become as an innovative and
alternative approach to improve the performance of the mem-
branes [4].
Organicinorganic hybrid membranes are formed by the addi-
tionof inorganic oxideparticles inmicrometer as well as nanometer
sizes to polymeric casting solutionor by insitugeneration. Over the
past fewyears, suchtypes of membranes have receivedmuchinter-
est inthe relevant membrane processes suchas reverse osmosis [5],

Corresponding author. Tel.: +91 431 2503118; fax: +91 431 2500133.
E-mail addresses: arthanareeg@nitt.edu, arthanaree10@yahoo.com
(G. Arthanareeswaran).
pervaporation [6], ultraltration [7] and nanoltration [8]. Many
researchers have developed organicinorganic hybrid membranes
using a variety of inorganic particles such as silica (SiO
2
), alumina
(Al
2
O
3
), zirconia (ZrO
2
) and titania (TiO
2
) [913] with a variety of
polymers. The resultant hybrid membranes have been reported
to increase ux as well as mechanical strength upon increasing
the concentration of inorganic particles. Amongst different kinds
of inorganic particles, zirconia is known to have great chemical
resistance, thermal stability, permeability and ux compared to
silica, alumina and titania [14,15]. However, studies on the use
of zirconia microparticles in the preparation of organicinorganic
hybrid membranes are limited and with grain sizes in nanome-
ter range are still unknown [4]. Bottino et al. [16] added different
amounts of ZrO
2
particles into polyvinylidene uoride (PVDF) and
shown that an increase of the ZrO
2
concentration leads to the
increase in permeation ux. Genne et al. [17] prepared a poly-
sulfone (PSf)/ZrO
2
composite membrane and reported that the
permeability increases and the rejection of dextran decreases upon
addition of increasing amounts of ZrO
2
to the membrane casting
solution. Doyen et al. [18] compared the basic membrane prop-
erties of the PSf/polyvinyl pyrrolidone, zirconia and zirconia/PSf
hybrid membranes and concluded that the membranes made up of
organo-mineral composition show an improved performance.
Cellulose acetate (CA) based membranes are suitable for UF
applications because of their moderate ux, moderate salt rejec-
1383-5866/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2010.06.010
G. Arthanareeswaran, P. Thanikaivelan / Separation and Purication Technology 74 (2010) 230235 231
tion and good lm forming properties. Further, they are relatively
easy to manufacture, cost effective and highly non-toxic. However,
CA has poor chemical resistance, fouling resistance, thermal sta-
bility and mechanical strength. Thus, the modication of CA gains
importance [19]. Although blending of CA with other organic poly-
mers is widely examined, studies on the use of inorganic particles
for the preparation of CA-inorganic hybrid membranes are lim-
ited. Wara et al. [20] studied the effect of alumina particles on the
microstructure of CA/Al
2
O
3
blend membranes. We have recently
developed CA/SiO
2
hybrid membranes and shown that the fouling
resistance of the membranes increased greatly as the SiO
2
con-
tent increased in the casting solution [21]. The effect of addition of
additives on the CA/SiO
2
hybrid membranes has also been studied
[22]. Hence, in this investigation, an attempt has been made to pre-
pare at sheet organo-mineral composite membranes composed
of organic (CA) and inorganic microparticles (ZrO
2
) using phase-
inversion technique. The effects of addition of ZrO
2
microparticles
on the membrane properties were investigated by examining the
UF performances such as pure water ux and membrane resis-
tance. The pore size, porosity and pore size distribution as well as
mechanical strength of the prepared membranes were examined.
Morphology, ability to resist fouling as well as recyclable property
of the selected membranes was also studied.
2. Experimental
2.1. Materials
Commercial grade CA was procured from Mysore Acetate and
Chemicals Co. Ltd., India and used after recrystallization from ace-
tone. Acetone of analytical grade was procured fromSisco Research
Ltd., India. N,N

-dimethylformamide (DMF) and sodium lauryl sul-

fate (SLS) were obtained from Qualigens Fine Chemicals, Glaxo
India Ltd., India, which were of analytical grade. DMF was sieved
through molecular sieves (Type-4 A

) to remove moisture and

stored in dry condition prior to use. Zirconia (ZrO
2
) was obtained
fromSDFine Chemical Ltd., India (average primary particle size was
19m, as reported by the manufacturer). Proteins such as trypsin,
pepsin, and bovine serumalbumin (BSA) were obtained fromSisco
Research Ltd., India. Egg albumin was obtained from Central Drug
House, India. Mono-sodium di-hydrogen ortho phosphate and di-
sodium hydrogen ortho phosphate were procured from Central
Drug House, India.
2.2. Membrane preparation
The casting solution was prepared by dissolving CA in DMF sol-
vent in a round bottom ask and ZrO
2
microparticles were added
and subjected to constant stirring for 4h at room temperature to
obtain a homogenous solution. Membranes were prepared using
phase-inversion technique as explained elsewhere [21]. Different
concentrations of ZrO
2
ranging from0 to 7wt.% were blended with
17.510.5wt.% of CA, respectively in presence of 82.5wt.% DMF as
shown in Table 1. The ratio of CA:ZrO
2
studied were pure CA, 9:1,
8:2, 7:3 and 6:4. These CA:ZrO
2
compositions were labeled as CA-0,
CA-1, CA-2, CA-3, and CA-4, respectively. The excess addition of
ZrO
2
(above 7wt.%) causes incomplete formation of the mem-
brane. Hence, the upper limit of the zirconia concentration was
maintained at 7wt.%. The membranes formed were washed with
distilled water and stored in the 0.1wt.% formalin solution to avoid
microbial attack.
2.3. Experimental set up
All the experiments for the UF characterization of the prepared
membranes were carried out in a batch type, dead-end cell (ultra-
ltration cell-S76-400-Model, Spectrum, USA) with a diameter of
76mm and effective membrane ltration area of 38.5cm
2
tted
withTeoncoated magnetic paddle. While carrying out the protein
rejection studies, a constant agitation speed of 300rpm was used
in to order to reduce concentration polarization of the membranes.
2.4. UF characterization
2.4.1. Pure water ux (PWF)
The experiment was carried out at a transmembrane pressure of
345kPa and the permeate was collected. The PWF was calculated
using Eq. (1) as below.
J
w1
=
Q
t A
(1)
where J
w1
is the pure water ux (lm
2
h
1
); Q is the amount of
permeate collected (l); t is the sampling time (h) and A is the
membrane area (m
2
).
2.4.2. Membrane resistance (R
m
)
The membrane resistance is the resistance offered by the mem-
brane to the feed ow. It is an indication of the tolerance of the
membrane towards hydraulic pressure and was calculated using
Eq. (2) as below [23].
R
m
=
P

w
J
w1
(2)
where R
m
is the membrane resistance (m
1
); P is the trans-
membrane pressure (345kPa);
w
is the viscosity of pure water
(8.410
4
Pa s).
2.4.3. Pore statistics
For studying the pore statistics, the proteins such as trypsin,
pepsin, egg albumin and BSA of different molecular weights were
used. From the protein rejection studies, the average pore radius,
surface porosity and pore density of the membranes were calcu-
lated. The average pore radius was found using Eq. (3) [22].

R =

%SR
100 (3)
where

R is the average pore radius () of the membrane; is the
average solute radius () andis constant for eachmolecular weight.
The average solute radii is known as stoke radii and the value of
canbe foundfromthe plot betweenthe solute radius andmolecular
weight of the solute as given by Sarbolouki [24] which is shown
Table 1
The compositions of casting solution for preparing CA:ZrO
2
hybrid membranes.
Membrane type Compositions (wt.%) DMF (wt.%) CA:ZrO
2
ratio
CA ZrO
2
CA-0 17.5 0 82.5 Pure CA
CA-1 15.75 1.75 82.5 9:1
CA-2 14.0 3.5 82.5 8:2
CA-3 12.25 5.25 82.5 7:3
CA-4 10.5 7.0 82.5 6.4
232 G. Arthanareeswaran, P. Thanikaivelan / Separation and Purication Technology 74 (2010) 230235
Table 2
Average solute radius and molecular weight of the selected proteins.
Protein Molecular weight (kDa) Average solute radius
a
()
Trypsin 20 21.5
Pepsin 35 28.5
Egg albumin 45 33.0
BSA 69 45.0
a
Values given by Sarbolouki [24].
in Table 2. Assuming the membrane to be asymmetric type, the
surface porosity of the membrane was found using Eq. (4).
=
3
w
J
w1
R P
(4)
where is the surface porosity;
w
is the viscosity of the deion-
ized water (g/cms); J
w1
is the pure water ux (cm/s) and P is the
applied pressure (dyn/cm
2
). From the values of and

R (cm), the
pore density in the membrane surface was calculated using Eq. (5).
n =



R
2
(5)
where n is number of pores/cm
2
.
2.5. Protein rejection studies
The protein rejection study was carried out using the pro-
tein solutions of different molecular weight. The protein of lowest
molecular weight such as trypsin was used rst in order to reduce
the fouling of the membranes followed by proteins with higher
molecular weight. The protein solutions were prepared as reported
earlier [25]. The pH of the buffer solution was maintained at 7.2,
since any change in the pH may lead to adsorptive fouling of the
membrane surface [26]. The concentration of the feed (C
p
) and
the permeate (C
f
) was found using UVvisible double beam spec-
trophotometer (Elica, SL 164, Double Beam) at
max
=280nm. The
solute rejection was found by Eq. (6).
%SR = 1
C
p
C
f
100 (6)
2.6. Mechanical stability
Two dumbbell shaped specimens of 5mm wide and 10mm
gauge length, were cut out of each membrane. Mechanical stud-
ies such as tensile load, tensile stress and percentage elongation
at break were carried out using Instron 4500 universal testing
machine at an extension rate of 2mm/min.
2.7. Morphological studies
The top surface and cross-sectional morphology of the CA:ZrO
2
hybrid membranes were studied using SEM (JEOL JSM-6360). The
membranes were cut into pieces of various sizes, mopped with
lter papers, immersed in liquid nitrogen for few seconds, and
were frozen. The samples were mounted on the sample holders
and platinum sputtered to provide electrical conductivity to the
membranes.
2.8. Fouling-resistant ability
After 4h of ultraltration of BSA solution, the membranes were
washed with deionized water for 20min and the water ux of the
cleaned membranes was measured (J
w2
) at 345kPa. In order to
evaluate the fouling-resistant ability of the blend membranes, ux
recovery ratio (FRR) was calculated [21] using equation
%FRR =
J
W2
J
W1
100 (7)
To measure the degree of fouling for CA:ZrO
2
membranes, we
dene the fouling resistance in terms of reversible and irreversible
fouling resistance of the membranes. For a simple dead-end UF
process, Darcys law was suitable to characterize the fouling.
J =
P
R
t
(8)
R
t
= R
m
+R
f
= R
m
+R
r
R
ir
(9)
where, R
t
is the total resistance (m
1
); and R
f
is the total fouling
layer resistance (m
1
). In general, R
f
is composed of both reversible
(R
r
) and irreversible fouling resistance (R
ir
). The fouling that can
be removed by hydrodynamic methods such as backwashing and
cross-ushing of the membranes is reversible fouling. The fouling
that cannot be removed by hydrodynamic method is dened as
irreversible fouling [27]. All these resistances are calculated from
following equations:
R
f
=
P
J
p
R
m
(10)
R
r
=
P

1
J
w2

1
J
w1

(11)
R
ir
= R
f
R
r
(12)
where R
m
is the membrane resistance (m
1
);
w
is the viscosity of
deionized water (8.910
4
Pa s).
2.9. Recyclable property of hybrid membranes
In order to test the recyclable potential of CA:ZrO
2
membranes,
three repetitive UF operations were carried out using BSA solu-
tion at 345kPa. This recycling experiment included four times run
of pure water ux and three times run of BSA solution ux using
dead-end UF cell. The membranes were cleaned with water each
time after nding the ux with BSA solution, and subjected to pure
water ux. The process was stopped after four runs, because the
BSAmolecules foul onthe membrane surface andthe ux remained
constant.
3. Results and discussion
3.1. Pure water ux
The water ux is an essential parameter for the membranes,
which is useful for any industrial process. The pure water ux of
the CA:ZrO
2
hybrid membranes was studied at 345kPa and shown
in Table 3. The pure CA membrane showed the lowest value of
pure water ux of 15.58lm
2
h
1
at 345kPa. The lower PWF value
may be due to the compact polymer matrix formed with pure CA.
The incorporation of ZrO
2
in CA membrane up to 7wt.% (CA-4),
increased the pure water ux value up to 46.74lm
2
h
1
which is
due tothe macrophase separationof the components that enhances
the pore size of the membrane [28]. The increase in PWF may also
be attributed to the increase in efcient ltration area due to the
addition of inorganic zirconia particles and their accumulation on
the membrane surface [29].
3.2. Membrane resistance
Inorder to determine the membrane resistance, the membranes
prepared from pure CA and CA:ZrO
2
were subjected to transmem-
brane pressure of 345kPa, under steady state ux condition. The
linear proportionality of pure water ux to applied pressure can be
G. Arthanareeswaran, P. Thanikaivelan / Separation and Purication Technology 74 (2010) 230235 233
Table 3
The pure water ux, solute permeability, resistances and ux recovery ratio of CA:ZrO
2
membranes.
Membrane type PWF (lm
2
h
1
) Solute ux (lm
2
h
1
) Rm (10
9
m
1
) Fouling layer
resistance (10
10
m
1
)
FRR %
Trypsin (20kDa) Pepsin (35kDa) EA (45kDa) BSA (69kDa) R
f
Rr R
ir
CA-0 15.58 14.17 11.95 8.75 5.19 2.70 7.19 5.60 1.59 61
CA-1 20.25 16.87 14.19 11.95 11.33
CA-2 24.93 21.3 16.87 15.96 14.15 1.50 3.72 3.01 0.71 66
CA-3 43.62 22.33 18.39 17.79 17.3
CA-4 46.74 26.45 24.54 23.85 19.79 0.90 2.58 2.24 0.34 71
directly related to the transport resistance. As seen in Table 3, it is
evident that the CA-0 membrane shows higher membrane resis-
tance of 2.7010
9
m
1
. In general, the R
m
values were decreased
when the zirconia content was increased from 0 to 7wt.% in the
casting solution. In particular, when ZrO
2
content was increased
to 3.5wt.%, the membrane resistance decreased to 1.5010
9
m
1
.
While a further increase in ZrO
2
content to 7wt.% resulted in the
lowest membrane resistance of 0.9010
9
m
1
. This decrease in
R
m
may be due to the fact that increasing the concentration of ZrO
2
in the casting solution not only increases the amorphous nature
of the membranes but also enhances the pore size to a greater
extent leading to an extended volume fraction between polymer
chains thereby decreasing the value of R
m
[19]. This is because the
degree of miscibility of the blend components is an important fac-
tor. At 6:4 ratio of CA:ZrO
2
, the degree of miscibility is at a critical
level, beyond which microseparation may start and phase separa-
tion may take place at a faster rate. Hence, it is very difcult to
achieve uniform membranes above 7wt.% of ZrO
2
content.
3.3. Pore statistics
As is observed from Table 4, the average pore radius of pure
CA membrane is 26.88. It is seen that adding 7wt.% of ZrO
2
in
the casting solution enhances the pore radius in the membrane to
47.52 due to the aggregation of ZrO
2
particles or the weak bond-
ing between membrane and microparticles. Surface porosity ()
provides total pore area per unit surface area of the membrane.
As seen from Table 4, the value of is found to be 5.7210
5
for
pure CA membrane without ZrO
2
particles. When the inorganic
content was increased to 7wt.% in the CA polymeric matrix, the
surface porosity increased steeply to 10.5810
5
. Consequently,
the water ux through such porous membranes is expected to
increase signicantly with reduced retention. These results are in
good agreement with the pure water ux data. Genne et al. [17]
obtained similar results when zirconia was added to PSf blend
membranes.
When pure CA membrane is compared with the 6:4 CA:ZrO
2
hybrid membrane, the value of pore density increased from
6.7710
9
to 8.3610
9
. These results show that the addition of
ZrO
2
particles in the casting solution causes the formation of
numerous pores due to the aggregation of ZrO
2
particles. Aggre-
gated ZrO
2
particles may disrupt the polymer chain packing thus
increasing the free volume thereby enhancing the porosity [30].
3.4. Protein permeate ux
Protein ux is a measure of the product rate of the mem-
brane for a given protein solution. The effect of addition of
ZrO
2
particles in the polymer matrix in terms of protein per-
meate ux is shown in Table 3. The permeate ux of pure
CA membrane (CA-0) is 14.17lm
2
h
1
for trypsin and declined
up to 5.19lm
2
h
1
for BSA. The decrease in permeate ux
may be due to the fact that the highest molecular weight
solutes (BSA) are retained by the membrane whereas the lowest
molecular weight solutes (trypsin) pass through the membranes
easily. When the concentration of zirconia in the membrane is
increased to 7wt.%, the permeate ux for trypsin increased to
26.45lm
2
h
1
and for BSA it increased to 19.79lm
2
h
1
. The
increase in permeate ux may be due to the increase in poros-
ity and hydrophilicity of the membrane owing to the addition
of 7wt.% ZrO
2
. Similar results were obtained elsewhere also
[16,17].
3.5. Mechanical stability
It is interesting to note that the load, stress and elonga-
tion at break values tend to increase upon the addition of
1.75wt.% of ZrO
2
to 15.75wt.% CA membrane, as seen in Table 4.
However, further addition of ZrO
2
particles up to 7wt.% with
reducing CA content resulted in decreasing mechanical stabil-
ity of the hybrid membranes. The initial increase may be due
to the increase in dense-layer thickness and interaction between
inorganic particles and polymers. However, an excessive con-
centration may cause the aggregation of particles and prevent
them to disperse uniformly in polymeric matrix, which acts as
weak links thereby declines the mechanical stability of mem-
brane. Yan et al. [11] also observed similar trends in terms of
tensile strength and elongation at break for Al
2
O
3
/PVDF blend UF
membranes.
3.6. Morphological study
SEM images of the cross-sections of the selected CA:ZrO
2
(pure
CA, 8:2 and 6:4 ratio) membranes are shown in Fig. 1. The arrow
mark shown in gure indicates the top surface of the membranes.
In general, it is seen that the membrane structure is not affected
by the addition of ZrO
2
microparticles, especially the continuity
Table 4
Pore statistics and mechanical stability of the CA:ZrO
2
hybrid UF membranes.
Membrane type Average pore
radius, R ()
Surface porosity,
10
5
Pore density,
number of
pores/cm
2
, 10
9
Tensile load (N) Tensile stress
(N/mm
2
)
Elongation at break
(%)
CA-0 26.88 5.72 6.77 3.070 2.047 8.84
CA-1 33.93 5.58 6.98 3.394 2.263 9.23
CA-2 35.95 6.91 7.37 2.519 1.679 7.08
CA-3 38.82 9.75 7.99 2.118 1.412 6.29
CA-4 47.52 10.58 8.36 2.063 1.375 6.13
234 G. Arthanareeswaran, P. Thanikaivelan / Separation and Purication Technology 74 (2010) 230235
Fig. 1. Scanning electron microscopic view of the cross-section of (a) pure CA, (b)
CA:ZrO
2
=8:2 and (c) CA:ZrO
2
=6:4 membranes.
between the membrane surface, skin layer and porous layer is
not affected, suggesting that the synthesized hybrid membranes
were homogeneous in nature and hence formed as dense mem-
branes (SEM images of membrane surfaces are not shown). In
Fig. 1a, the typical asymmetric pore structure with skin layer and
underneath ngerlike cavities of a pure CA membrane is seen.
In contrast to the pore structure of pure CA membrane, CA:ZrO
2
hybrid membranes (Fig. 1b and c) contain increasing pore size
across the cross-section as the zirconia content in the mem-
brane increases. The distribution of the ZrO
2
on the membrane
enabled the formation of nger like macropores linked by the
sponge walls. This observation is also in agreement with the pore
statistics studies. Doyen et al. [18] made a similar observation by
comparing the morphologies of the PSf/PVP and ZrO
2
/PSf blend
membranes.
3.7. Analysis of membrane fouling during ultraltration
The effects of membrane fouling and concentration polariza-
tion were usually observed by a considerable decline in the ux
with time under constant pressure. In this study, the concentration
polarization due to high molecular weight of BSA molecules was
minimized because of rigorous stirring near the membrane surface.
The membrane resistance due to the fouling after BSA separation
and cleaning of BSA was calculated for selected CA:ZrO
2
hybrid
membranes and shown in Table 3. As is evident from Table 3, the
total fouling resistance of pure CA membrane is 7.1910
10
m
1
.
With the increase of ZrO
2
concentration in the casting solution
to 7wt.%, the total fouling resistance of the CA:ZrO
2
membrane
decreased to 2.5810
10
m
1
. This decrease in fouling resistance
may be due to the increase in hydrophilicity of CA membrane
with the addition of ZrO
2
particles in the casting solution thereby
increasing the interactions of the BSAmolecules on membrane sur-
face. It is also observed from Table 3 that the membrane fouling is
dominated by the resistance offered by reversible fouling which
can be reduced by hydrodynamic methods such as backwashing
and cross-ushing of the membrane. Wang et al. [23] made simi-
lar observation for PES/pluronic P123 blend membranes. It is seen
that the FRR value for pure CA membrane is 61% whereas this value
is increased to 71% for CA:ZrO
2
hybrid membrane prepared in the
ratio of 6:4. Higher FRR value suggests that protein induced foul-
ing is reversible because of the increased hydrophilicity of CA:ZrO
2
hybrid UF membrane. Wang et al. [31] made similar observations
for PES/sulfobetaine copolymer blend membranes.
3.8. Recycling of the hybrid membranes
It is expected that the enhanced ux recovery property of
CA:ZrO
2
hybrid membranes will improve the membrane lifetime
without affecting the separation performances of the membrane.
To study the recycling potential of the CA:ZrO
2
hybrid membranes,
three cycles of UF of BSA solution were carried out and the results
are shown in Fig. 2. In case of CA-0, the initial water ux was
15.58lm
2
h
1
and subsequently decreased to 9.1lm
2
h
1
after
three runs of BSA solution. When the concentration of ZrO
2
in
CA:ZrO
2
membrane is increased to 7wt.%, the initial water ux
Fig. 2. Flux variation of CA:ZrO
2
hybrid membranes during three cycles of ultral-
tration of BSA solution.
G. Arthanareeswaran, P. Thanikaivelan / Separation and Purication Technology 74 (2010) 230235 235
was 46.74lm
2
h
1
. After four runs of water ux and three runs
of BSA solution ux, the water ux reached a steady state value
of 29lm
2
h
1
. Higher ux even after three runs of BSA solu-
tion demonstrates higher cleanability and improved anti-fouling
characteristics of hybrid CA:ZrO
2
membranes compared to pure
CA membrane. This may be due to the increased hydrophilicity
of CA:ZrO
2
hybrid membranes that reduces the membrane foul-
ing [32]. Wang et al. [33] made similar observations for PES and
pluronic polymer UF membranes.
4. Conclusions
In this investigation, the organo-mineral membranes were pre-
pared using cellulose acetate and zirconia as blend components
in DMF by phase-inversion technique. The UF performance of
CA:ZrO
2
membranes reveals that the pure water ux was increased
while the membrane resistance decreased, as the concentration
of ZrO
2
in the casting solution increased. The mechanical stabil-
ity of the CA:ZrO2 hybrid UF membranes were found to increase
with low concentration of ZrO
2
; however further increase in
ZrO
2
concentration resulted in decreased mechanical stability of
the UF membranes. The morphological studies show that the
pore formation increased with the addition of inorganic parti-
cles (ZrO
2
) to the polymer (CA). The anti-fouling ability of the
CA:ZrO
2
hybrid membranes enhanced considerably due to the
addition of inorganic particle to the casting solution. Especially,
the irreversible membrane fouling decreased signicantly with an
increase of ZrO
2
concentration in the casting solution. It has been
demonstrated that the excellent ux recovery property improved
the recyclable potential of CA:ZrO
2
hybrid membranes consider-
ably.
Acknowledgement
We would like to thank Dr. D. Mohan, Professor in Chemistry,
Department of Chemical Engineering, Anna University Chennai for
his technical support to complete this work.
References
[1] Z. Fan, Z. Wang, N. Sun, J. Wang, S. Wang, Performance improvement of poly-
sulfone ultraltration membrane by blending with polyaniline nanobers, J.
Membr. Sci. 320 (2008) 363.
[2] X. Fu, H. Matsuyama, M. Teramoto, H. Nagai, Preparation of polymer blend
hollow ber membrane via thermally induced phase separation, Sep. Purif.
Technol. 52 (2006) 363.
[3] J. Han, W. Lee, J.M. Choi, R. Patel, B.R. Min, Characterization of polyether-
sulfone/polyimide blend membranes prepared by a dry/wet phase inversion:
precipitationkinetics, morphologyandgas separation, J. Membr. Sci. 351(2010)
141.
[4] J. Kim, B. Van der Bruggen, The use of nanoparticles and nanotubes in poly-
meric and ceramic membrane structures: review of envisaged performance
improvements for water treatment, Environ. Pollut. 158 (2010) 2335.
[5] S.H. Kwak, S.H. Kim, Hybrid organic/inorganic reverse osmosis (RO) mem-
brane for bactericidal anti-fouling. 1. Preparation and characterization of TiO
2
nanoparticle self-assembled aromatic polyamide thin-lm-composite (TFC)
membrane, Environ. Sci. Technol. 35 (2001) 2388.
[6] K.S. Roelofs, T. Hirth, T. Schiestel, Sulfonated poly(ether ether ketone)-based
silica nanocomposite membranes for direct ethanol fuel cells, J. Membr. Sci.
346 (2010) 215.
[7] Z.Q. Huang, K. Chen, S.N. Li, X.T. Yin, Z. Zhang, H.T. Xu, Effect of ferrosoferric
oxide content on the performances of polysulfoneferrosoferric oxide ultral-
tration membranes, J. Membr. Sci. 315 (2008) 164.
[8] S. Darvishmanesh, A. Buekenhoudt, J. Degreve, B.V. Bruggen, General model
for prediction of solvent permeation through organic and inorganic solvent
resistant nanoltration membranes, J. Membr. Sci. 334 (2009) 43.
[9] Z. Pinnau, A. He, Morisato, Nanostructured poly(4-methyl-2-pentyne)/silica
hybrid membranes for gas separation, Polym. Mater. Sci. Eng. 85 (2001) 299.
[10] S. Liu, R. Highes, Preparation of porous aluminum oxide hallow bre mem-
branes by a combined phase-inversion and sintering method, Ceramic Int. 29
(2003) 875.
[11] L. Yan, Y.S. La, C.B. Xiang, S. Xianda, Effect of nano-sized alumina particle addi-
tion of PVDF ultraltration membrane performance, J. Membr. Sci. 276 (2006)
162.
[12] G. Bottino, V. Capannelli, D. Asti, P. Piaggio, Preparation, and properties of novel
organic-inorganic porous membranes, Sep. Purif. Technol. 22 (2001) 269.
[13] Y. Yang, H. Zhang, P. Wang, Q. Zhang, J. Li, The inuence of nano-sized TiO
2
llers on the morphologies and properties of polysulfone UF membranes, J.
Membr. Sci. 288 (2007) 231.
[14] C. Yang, G. Zhang, N. Xu, J. Shi, Preparation and application in oilwater sepa-
ration of ZrO
2
/-Al
2
O
3
MF membrane, J. Membr. Sci. 142 (1998) 235.
[15] A. Larbot, J.P. Fabre, C. Guizard, L. Cot, G. Gillot, New inorganic ultraltration
membranes: titania and zirconia membranes, J. Am. Ceram. Soc. 72 (1989) 257.
[16] A. Bottino, G. Capannelli, A. Comite, Preparation and characterization of novel
porous PVDFZrO
2
composite membranes, Desalination 146 (2002) 35.
[17] I. Genne, S. Kuypers, R. Leysen, Effect of the addition of ZrO
2
to polysulfone
based UF membranes, J. Membr. Sci. 113 (1996) 343.
[18] W. Doyen, W. Adriansens, B. Molenberghs, R. Leysen, A comparison between
polysulfone, zirconia, and organo-mineral membranes for use inultraltration,
J. Membr. Sci. 113 (1996) 247.
[19] R.E. Kesting, Synthetic Polymeric Membranes, in: A Structural Perspective, 2nd
ed., New York, Wiley, 1985.
[20] N.M. Wara, L.F. Francis, B.V. Velamakanni, Addition of alumina to cellulose
acetate membranes, J. Membr. Sci. 104 (1995) 43.
[21] G. Arthanareeswaran, T.K. Sriyamuna Devi, M. Raajenthiren, Effect of silica par-
ticles on cellulose acetate blend ultraltration membranes. Part I, Sep. Purif.
Technol. 64 (2008) 38.
[22] G. Arthanareeswaran, T.K. Sriyamuna Devi, D. Mohan, Development character-
ization and separation performance of organicinorganic membranes. Part II.
Effect of additives, Sep. Purif. Technol. 67 (2009) 271.
[23] Y.Q. Wang, Y.L. Su, Q. Sun, X.L. Ma, Z.Y. Jiang, Generation of anti-fouling ultral-
tration membrane surface by blending novel branched amphiphilic polymers
with polyethersulfone, J. Membr. Sci. 286 (2006) 228.
[24] M.N. Sarbolouki, General diagram for estimating pore size of UF and RO mem-
branes, Sep. Sci. Technol. 17 (1982) 381.
[25] G. Arthanareeswaran, D. Mohan, M. Raajenthiren, Preparation, characterization
andperformance studies of ultraltrationmembranes withpolymeric additive,
J. Membr. Sci. 350 (2010) 130.
[26] J. Brinck, A.S. Jonsson, B. Jonsson, J. Lindau, Inuence of pH on the adsorptive
fouling of ultraltration membranes by fatty acid, J. Membr. Sci. 164 (2000)
187.
[27] J. Peirccia, J.V. Crivello, G. Belfort, Increasing membrane permeability of UV-
modied poly (ether sulfone) ultraltration membranes, J. Membr. Sci. 202
(2002) 1.
[28] H. Yasuda, J.T. Tsai, Pore size of microporous polymer membranes, J. Appl.
Polym. Sci. 18 (1974) 805.
[29] Y.S. Li, L. Yan, C.B. Xiang, L.J. Hong, Treatment of oily wastewater by
organicinorganic composite tubular ultraltration (UF) membranes, Desali-
nation 196 (2006) 76.
[30] P. Aerts, I. Genne, S. Kuypers, R. Leysen, I.F.J. Vankelecom, P.A. Jacobs,
Polysulfoneaerosil composite membranes. Part 2. The inuence of the addi-
tion of aerosil on the skin characteristics and membrane properties, J. Membr.
Sci. 178 (2000) 1.
[31] T. Wang, Y.Q. Wang, Y.L. Su, Z.Y. Jiang, Antifouling ultraltration membrane
composed of polyethersulfone and sulfobetaine copolymer, J. Membr. Sci. 280
(2006) 343.
[32] L. Yan, Y.S. Li, C.B. Xiang, Preparation of poly (vinylidene uoride) (PVDF)
ultraltration membrane modied by nano-sized alumina (Al
2
O
3
) and its
antifouling research, Polymer 46 (2005) 7701.
[33] Y.Q. Wang, Y.L. Su, X.L. Ma, Q. Sun, Z.Y. Jiang, Pluronic polymers and
polyethersulfone blend membranes with improved fouling-resistant ability
and ultraltration performance, J. Membr. Sci. 283 (2006) 440.