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Article history: This paper deals with the preparation of organic–inorganic ultrafiltration (UF) membranes by solution
Received 26 April 2007 casting followed by phase separation method. The silica (SiO2 ) particles were added to the cellulose acetate
Received in revised form 22 July 2008 (CA) polymer with the increment of 10 wt.% from 0 to 40% by weight using N,N-dimethyl formamide (DMF)
Accepted 24 August 2008
as polar solvent. The prepared organic–inorganic membranes were characterized for UF performance such
as compaction, pure water flux, % water content, membrane hydraulic resistance, molecular weight cut-
Keywords:
off (MWCO) and pore statistics. MWCO and pore statistics were investigated using protein solutions of
Organic–inorganic membrane
different molecular weights. It is observed that by increasing the concentration of SiO2 in CA polymer, the
Pore statistics
Membrane morphology
MWCO, pore radius, surface porosity and pore density has been increased. The mechanical stability of the
Protein separation CA/SiO2 blend membranes increased initially and then declined with the addition of inorganic particle
Membrane fouling-resistant ability above 10 wt.% to the casting solution. The morphological structure was changed with the addition of SiO2
particles in the casting solution. Further the permeate flux and % rejection of different molecular weight of
proteins were investigated which showed an increased protein permeate flux with the decreased solute
rejection. Meanwhile, the effect of SiO2 content in the CA membranes on fouling-resistant ability was
studied using BSA solution. The results indicated that increasing the SiO2 content in the casting solution,
the reversible fouling resistance dominated the total fouling resistance thereby improving the fouling
resistance ability of the blend membranes.
© 2008 Elsevier B.V. All rights reserved.
1383-5866/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2008.08.010
G. Arthanareeswaran et al. / Separation and Purification Technology 64 (2008) 38–47 39
of fine silica particles in the porous matrix of polyvinylidenefluo- the CA (17.5 wt.%, by weight of the solution) in the DMF as sol-
ride (PVDF) and observed that with the increasing concentration of vent at room temperature and adding fumed SiO2 particles to the
SiO2 in PVDF, the permeate flux increased with the lowered pro- casting dopes while stirring. For the organic–inorganic membranes
tein retention. Yan et al. [18] prepared blend membranes based (CA–SiO2 ), the CA polymer was first dissolved in the solvent and
on PVDF and alumina (Al2 O3 ) materials by phase inversion pro- then thoroughly mixed with the SiO2 . Special care was taken to
cesses and characteristic studies like membrane hydrophilicity, ensure homogeneous dispersion of the SiO2 particles. The concen-
porosity, protein retention and surface morphologies were inves- tration of SiO2 added to CA varied from 0 to 40 wt.%, beyond the
tigated. It was observed that the permeation flux increase of the 40 wt.% resulted in the turbid form and did not form the mem-
membrane is attributed to surface hydrophilicity increase due to brane. This may due to concentration of CA in the casting solution
the hydrophilic inorganic nano-sized Al2 O3 particles addition. Yang was reduced below 60 wt.%, in other words the polymer rich phase
et al. [13] prepared PSf/TiO2 organic–inorganic composite mem- became very weak in the membrane formation, which in turn lead
branes via phase-inversion process and observed that with the to the inhibition of membrane formation. In order to obtain optimal
addition of TiO2 particles to polymer casting solution resulted in dispersions of the particles in the polymer solutions, agitation was
the increased pore numbers in the skin layer and the hydrophilic- required for at least 24 h. The casting solutions were then kept for
ity also improved apparently that enhanced the pure water flux. The 24 h to remove air bubbles. The polymer solution with SiO2 parti-
mechanical strength of membrane was enhanced through adding cles was kept in dehumidifying chamber with a relative humidity
inorganic fillers, especially, at 2 wt.% filler concentration, the burst- of 60 ± 5%. The solution was then casted over a glass plate with the
ing strength and the breaking strength increased 50% and 26.7%, help of doctor blade. The thickness of prepared membranes was
respectively. Wara et al. [14] reported the fabrication of nano- measured in different places of membrane, the average membrane
composite membranes of Al2 O3 particles in CA by using the solution thickness was 0.2 ± 0.02 mm. This thickness is maintained for all
blending. We have examined consist of inorganic domains that are the membranes. The casted solution was then allowed to be in the
randomly dispersed with the polymer matrix. The presence of the chamber for 30 s for the evaporation of solvent from top surface of
inorganic phase can also serve to restrict the molecular motions the membrane. The casted membrane was then immersed in the
of the polymer chains and to induce an increase in the mean dis- gelation bath with water as non-solvent and DMF as solvent with
tance (free volume) between polymer chains. We postulate that the the addition of SLS as surfactant for 30 min for the leaching out of
restricted molecular motions and a favorable increase in the mean solvent from the membrane surface [20]. This method is commonly
distance between chains can lead to a simultaneous improvement known as phase inversion technique [21]. The formed membranes
in selectivity and permeability. were stored in the 0.1 wt.% formalin solution to avoid microbial
Hence, for the present study, SiO2 particles are blended with attack. The stepwise preparation of the polymeric membrane is
CA with an increment of 10 wt.% from 0 to 40 wt.% to obtain mem- shown in Fig. 1.
branes with improved quality in terms of UF characteristics such
as compaction, pure water flux, percent water content, membrane 2.3. Experimental set up
hydraulic resistance, and in terms of % solute rejection, MWCO,
pore statistics, mechanical stability and membrane morphology. The characterization methods were carried out in a batch type,
The fouling-resistance ability and the recycling of the CA/SiO2 blend dead end cell (ultrafiltration cell-S76-400-Model, Spectrum, USA)
membranes were evaluated through UF experiments using BSA as with a diameter of 76 mm and effective membrane filtration area of
model protein. Further, increase of SiO2 in CA is above 40 wt.%, 38.5 cm2 fitted with Teflon coated magnetic paddle. While carry-
resulted in the turbid form and the polymer phase separation ing out the protein rejection studies, a constant agitation of speed
occurred. Hence, the threshold limit of SiO2 is maintained to a 300 rpm was used in to order to reduce concentration polarization
maximum of 40 wt.% in CA blend composition. of the membranes. The cell was connected to a nitrogen cylinder
with the pressure control valve and gauge through a feed reservoir.
2. Experimental procedure
2.4. UF characterization
2.1. Materials
The prepared membranes were characterized for compaction,
The CA used was obtained from Mysore Acetate and Chemi- pure water flux, membrane hydraulic resistance, protein rejec-
cals Company Limited, India, and was used, after recrystallatization tion studies, fouling-resistant ability and recycling of the blend
from acetone. Analar grade N,N-dimethyl Formamide (DMF) was membranes using dead end UF experiment. The % water content,
obtained from was and sieved through molecular sieves for MWCO, pore statistics, mechanical stability and morphological
removing moisture and stored in dried condition. Fumed sil- studies were also investigated.
ica powders (hydrophilic silica powder, average primary particle
size = 0.014 mm) was purchased from Central Drug House, India 2.4.1. Compaction
and dried at 80 C before use. Sodium lauryl sulfate (SLS) used as The thoroughly washed membrane was cut into desired shape
surfactant was obtained from Sisco Research Limited, India. Pro- and fitted in UF kit. The distilled water was fed into the UF kit from
teins like trypsin, pepsin, and bovine serum albumin (BSA) were the pressure reservoir and the initial water flux was taken, 20 s after
also obtained from Sisco Research Limited, India. Egg albumin was the pressurization at 414 kPa [22]. The permeate was collected for
obtained from Central Drug House, India. Phosphate buffers like every 1 h of time interval till it attains steady state.
Mono-sodium di-hydrogen ortho phosphate and di-sodium hydro-
gen ortho phosphate were procured from Central Drug House, India. 2.4.2. Pure water flux (PWF)
After compaction, the experiment was carried out at a differ-
ential system pressure of 345 kPa and the permeate was collected
2.2. Solution blending and membrane formation
[22]. The PWF was calculated using the equation:
Table 1
Average solute radius of the proteins
Trypsin 20 21.5
Pepsin 35 28.5
Egg albumin 45 33.0
BSA 69 45.0
a
Values given by Sarbolouki [24].
Cp
%SR = 1 − × 100 (4)
Cf
Jw2
%FRR = × 100 (8)
Jw1
Jp
rt = 1 − (9)
Jw1
Here, rt was the degree of total flux loss caused by total fouling.
rr and rir were also defined to distinguish reversible fouling and
irreversible fouling. Reversible fouling ratio (rr ) describes the foul-
ing caused by concentration polarization and irreversible fouling
ratio (rir ) describes the fouling caused by adsorption or deposition
of protein molecules on the membrane surface. They are defined
by equations:
(Jw2 − Jp )
rr = (10)
Jw1 Fig. 2. Effect of compaction on pure water flux of CA/SiO2 blend UF membrane.
42 G. Arthanareeswaran et al. / Separation and Purification Technology 64 (2008) 38–47
Table 2
Effect of SiO2 concentration on CA blend membranes
Polymer (17.5 wt.%) Solvent (wt.%) PWF at 345 kPa (l m−2 h−1 ) Water content (%) Rm (kPa/l m−2 h−1 ) MWCO (kDa)
CA SiO2 DMF
blend ultrafiltration membranes. It is believed to form uniform, membrane to the feed flow. From Table 2, it is evident that the pure
rigid pores during compaction on the membrane surface and to 100 wt.% CA exhibited a higher value of 21.65 kPa/l m−2 h−1 due to
obtain a steady state flux. Similar trend was obtained for the mem- low porosity of the CA membrane. In the CA/SiO2 blend membranes,
branes with varying composition of 90/10, 80/20 and 70/30 wt.% when the concentration of SiO2 increased with 10 wt.% increments
of CA/SiO2 blend composition. Further, if any trace quantity of to a maximum of 40 wt.% in the casting solution, Rm value gradu-
solvent present in the membrane surface, which is pass through ally decreased to 7.15 kPa/l m−2 h−1 . The introducing of silica in the
the membrane along with the permeate during compaction. polymer chains is expected to be effective in promoting interface
void formation during the membrane preparation. The enhanced
3.2. Pure water flux (PWF) pore size of the CA/SiO2 membrane due to the extended free vol-
ume between the polymer chains by addition SiO2 resulted in the
After completion of compaction, the pure water flux of blend decrease of Rm value. Yang et al. [13] studied PSf/TiO2 blend mem-
membranes were studied at 345 kPa pressure and shown in Table 2. branes in terms of numerous pores on the membrane surface, which
The low pure water flux value of 15.58 l m−2 h−1 is obtained for is inversely proportional to the water flux of the respective mem-
100 wt.% CA membranes. This is because for the pure 100 wt.% CA, branes. Similar decrease in Rm values was obtained for the other
a very tight polymer matrix is formed, thus the pores formed on blend membranes with varying composition of CA/SiO2 as 90/10,
the membrane surface will be in smaller size. When the concentra- 80/20, 70/30 wt.%.
tion of SiO2 is increased from 10 to 40 wt.% in the pure CA blend
membrane, the PWF showed an increased value from 35.83 to 3.5. Molecular weight cut-off (MWCO)
46.74 l m−2 h−1 .
The increase in the pure water flux may be due addition of fumed The MWCO of a membrane corresponds to molecular weight of
silica particles to CA has been confirmed to systematically increase solutes that has the rejection of more than 80% [23]. MWCO of all
the average size of the free volume. Similar observations were made the membranes of varying composition of CA/SiO2 was determined
by He and Morisato [27], non-porous, nano-size fumed silica, was individually based on the study of protein rejection using proteins
incorporated into a PMP matrix. of different molecular weight and tabulated in Table 2. MWCO of the
100 wt.% CA is compared with the blend membranes with compo-
3.3. % Water content sition 90/10, 80/20, 70/30 and 60/40 wt.% of CA/SiO2 . It is evident
from Table 2 that the MWCO of the pure 100 wt.% CA membrane
Water content of the membrane relates hydrophilicity of the is 20 kDa. This is because the membrane formed of pure CA has
membrane [28]. The % water content was calculated using the Eq. smaller pores size due to the tight polymer matrix. Malaisamy et al.
(2) and the value of the membranes were shown in Table 2. From [30] obtained similar results for CA/Sulfonated polysulfone blend
Table 2, the % water content of 100 wt.% CA membrane showed a membranes. When considering the MWCO of the newly formed
value of 76.59%. In case of 60/40 wt.% of CA/SiO2 blend membrane, blend membrane of 90/10 wt.% CA/SiO2 showed a higher value of
the percent water content was 82.56%. When the 40 wt.% SiO2 par- 35 kDa. With the further increase of 40 wt.% SiO2 to CA membrane,
ticles were present in the pure CA membrane, the water content of the MWCO further increased to 45 kDa. The increase in MWCO of
blend membrane was increased. Similar increase in water content the blend membranes may be due to the increase in free volume and
was interpreted by Lv et al. [12] when small amount of Pluronic a decrease in polymer chain segmental mobility by the presence of
F127 was incorporated into CA membranes. The increased water silica material in the polymer casting solution [31].
content may be due to the detachment of polymer chains from
the silica surface, causing the interface voids. Further, this leads 3.6. Pore statistics
to increase in void volume resulting in the formation of bigger
size pores on the membrane surface and increase the water uptake Pore statistics includes average membrane pore radius (Å), sur-
in the pores. Similar results were obtained by Yan et al. [18] for face porosity, and pore density. Average pore radius (R) of the
PVDF/Al2 O3 blend membranes which reveal that with the addi- membrane is found from the % solute rejection using the protein
tion of Al2 O3 particle to the PVDF blend membrane, the contact solutions prepared from trypsin, pepsin, EA, and BSA of 0.1 wt.%
angle decreased which showed an increase in hydrophilicity of the in phosphate buffers. The pure 100 wt.% CA membrane was com-
blend membranes which confirms an increased uptake of the water pared with the CA/SiO2 blend composition of 90/10, 80/20, 70/30,
through the membrane pores. and 60/40 wt.%. It is observed that for pure 100% CA, the value of
R is found to be 26.88 Å. The relation between the average mem-
3.4. Membrane hydraulic resistance (Rm ) brane pore radius and the concentration of silica in CA is plotted
in Fig. 3(a) and observed that the membrane average pore radius
In order to determine the membrane hydraulic resistance, the is 41.25 Å when the concentration of SiO2 is increased to 40 wt.% in
pure water flux was measured by varying the transmembrane pres- the CA membrane [16].
sure of the system to 414, 345, 276, 207, 138, 69 kPa. The value of Rm Surface porosity (ε) gives the detail about total pore area per
is calculated by Eq. (3), which reveals the resistance offered by the unit surface area of the membrane and calculated using Eq. (6).
G. Arthanareeswaran et al. / Separation and Purification Technology 64 (2008) 38–47 43
Table 3
Mechanical stability of the CA/SiO2 blend UF membranes
Composition (17.5 wt.%) Solvent (wt.%) Tensile intensity (N) Tensile stress (N/mm2 ) Break elongation ratio (%)
CA SiO2 DMF
meate flux may be due to the fact that solutes of lower molecular
weight pass through the smaller pore size membrane. When the
concentration of the SiO2 is decreased to 40 wt.% in the casting solu-
tion, the permeate flux for the given protein (e.g. BSA) increased to
19.79 l m−2 h−1 . The addition of fumed silica in CA pushes the per-
meability of the CA membrane towards a bigger pore size with high
permeability. Further incorporation of a small volume fraction of
inorganic fillers into the polymer matrix can result in a significant
increase in overall separation efficiency. The newly formed blend
membranes of 90/10, 80/20, 70/30 wt.% of CA/SiO2 showed a similar
increase in protein flux when other proteins like EA, pepsin, trypsin
were used individually. Sivakumar et al. [28] obtained decreased
protein flux when proteins of increasing molecular weights were
used for CA/PSf blend membrane.
Fig. 5. (a) SEM of the cross-sectional view of pure CA membrane; (b) SEM of the
cross-sectional view of 80/20 wt.% of CA/SiO2 blend UF membrane; and (c) SEM of
the cross-sectional view of 60/40 wt.% of CA/SiO2 blend UF membrane.
Table 4
The total fouling resistance (rf ), reversible resistance (rr ), irreversible resistance (rr ) and FRR value of different blend membranes using BSA solution
Composition (17.5 wt.%) Solvent (wt.%) Jw1 (l m−2 h−1 ) Jw2 (l m−2 h−1 ) Jp (l m−2 h−1 ) Fouling resistance ratio FRR %
polarization was minimized because of the high molecular weight 100 wt.% CA membrane, the initial water flux was 15.58 l m−2 h−1 .
of BSA molecules and rigorous stirring near the membrane surface. As the operation time increased, the water flux reached a steady
Therefore, the membrane fouling mostly caused the flux decline of state value of 9.1 l m−2 h−1 after three runs of BS solution flux. When
the membranes. Membrane fouling is caused by the adsorption or the concentration of SiO2 content in the CA membrane is increased
deposition of the protein molecules on the membrane surface. The to 40 wt.%, the initial water flux increased to 46.74 l m−2 h−1 . The
flux changes due to the fouling and cleaning of BSA were observed increase in permeation-flux of the CA/SiO2 blend membrane was
for 100/0, 80/20 and 60/40 wt.% of CA/SiO2 blend membranes is due to increase in the surface hydrophilicity and the efficient fil-
shown in Table 4. As seen from Table 4, the irreversible fouling tration area due to the addition of inorganic SiO2 particles [19].
ratio of 100 wt.% CA membrane is 0.39 and this value decreased After four runs of water flux and three runs of BSA solution flux,
to 0.25 with 40 wt.% of SiO2 in CA membrane which indicates that the water flux reached a steady state value of 27 l m−2 h−1 . This
the fouling of BSA on the membrane surface decreased. This may decrease in flux may be due to the fact that BSA particles foul the
be due to the fact that with the addition of inorganic particle to membrane surface. From the graph, it is evident that pure 100 wt.%
CA membrane, the hydrophilicity of the CA membrane is enhanced CA membrane can be used for two runs of BSA solution flux and
which reduces the interactions of the BSA particles on membrane 60/40 wt.% of CA/SiO2 blend membrane can be used for three runs
surface [19]. of BSA solution flux. This increase may be due to the increased
Since long time operation with the product rate was of great hydrophilicity of CA/SiO2 blend membranes that reduces the mem-
importance for practical application of membranes, FRR was intro- brane fouling [18]. The outstanding flux recovery property of blend
duced to evaluate the recycling property of the blend membranes. membranes indicates the long-run utilization and operation reli-
The FRR values for the CA/SiO2 blend membranes were calculated ability. Wang et al. [25] made similar observations for PES blend
using Eq. (8) and are presented in Table 4. It is observed that the membranes.
FRR values increased with the increase of SiO2 content in the casting
solution, and the maximum FRR value reached 75% for 60/40 wt.% 4. Conclusions
of CA/SiO2 blend UF membrane. This may be due to the increased
hydrophilicity [18] with addition of SiO2 content in CA blend mem- In this study, CA/SiO2 UF membranes were formed by phase
brane. inversion technique using DMF as solvent. The concentration of
SiO2 particles increased from 0 to 40 wt.% to CA membrane, above
3.11. Recycling of the blend membranes 40 wt.% did not form membrane. The prepared membranes were
studied for the UF performance such as compaction, PWF, mem-
The excellent flux recovery property of blend membranes will brane hydraulic resistance and percent water content. The UF
provide the long time membrane run without significant decline performance of CA/SiO2 membranes illustrates that the pure water
of separation performances. To study the recycling property of the flux and water content were increased, while the membrane
CA/SiO2 blend membranes, the graph is plotted between operation hydraulic resistance was decreased, as the concentration of SiO2
time vs. flux and the results are shown in Fig. 8. In case of pure in the casting solution is increased.
The MWCO was increased from 20 to 45 kDa with the increase
from 0 to 40 wt.% SiO2 concentration in the casting solution. The
gradual increase in average membranes pore radius, surface poros-
ity and pore density of CA/SiO2 membranes were observed when
compared with pure CA membrane. The mechanical stability of
the CA/SiO2 blend UF membranes were found using tensile testing
machine and observed that with the presence of inorganic parti-
cle of 10 wt.% in the casting solution, the mechanical stability in
terms of tensile intensity, tensile stress and break elongation ratio
increased, respectively. With the further increase of SiO2 particles
in the casting solution resulted in the decrease of the mechanical
stability of the UF membrane. The morphological studies were con-
ducted using SEM. It is observed that the pore formation increased
with the addition of inorganic grains (SiO2 ) to the polymer (CA)
membrane and change in morphological structure also observed.
The separation of protein studies also investigated using prepared
pure CA and CA/SiO2 UF membranes and observed that the rejec-
tion of protein molecules decreased with the enhanced permeate
flux as the concentration of SiO2 particles in the casting solu-
tion increased. The SiO2 content in CA/SiO2 blend membranes
enhanced the fouling-resistant ability thereby improving the recy-
Fig. 8. Flux variation of CA/SiO2 UF membranes during three times of BSA aqueous
cling ability of the CA/SiO2 blend membrane with increased FRR
solution. value.
G. Arthanareeswaran et al. / Separation and Purification Technology 64 (2008) 38–47 47
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