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Preparation and characterization of a novel


highly hydrophilic and antifouling
polysulfone/nanoporous TiO 2 nanocomposite
membrane

Article in Nanotechnology October 2016


DOI: 10.1088/0957-4484/27/41/415706

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Nanotechnology

Nanotechnology 27 (2016) 415706 (11pp) doi:10.1088/0957-4484/27/41/415706

Preparation and characterization of a novel


highly hydrophilic and antifouling
polysulfone/nanoporous TiO2
nanocomposite membrane
H Cheraghi Bidsorkhi1,2, H Riazi3, D Emadzadeh4,5, M Ghanbari1,
T Matsuura5, W J Lau1 and A F Ismail1
1
Advanced Membrane Technology Research Centre (AMTEC), Universiti Teknologi Malaysia, 81310
Skudai, Johor, Malaysia
2
Research Center for Nanotechnology Applied to Engineering of Sapienza (CNIS), Sapienza University of
Rome, Rome, Italy
3
Department of Polymer Engineering and Color Technology, Amirkabir University of Technology,
PO Box 15875-4413, Tehran, Iran
4
Department of Chemical Engineering, Gachsaran Branch, Islamic Azad University, Gachsaran, Iran
5
Industrial Membrane Research Laboratory, Department of Chemical and Biological Engineering,
University of Ottawa, 161 Louis Pasteur St, Ottawa, ON K1N 6N5, Canada

E-mail: d.emadzadeh@iaug.ac.ir and afauzi@utm.my

Received 19 November 2015, revised 20 July 2016


Accepted for publication 11 August 2016
Published 8 September 2016

Abstract
In this research, novel ultraltration nanocomposite membranes were prepared by incorporating
self-synthesized nanoporous titanium dioxide (NTiO2) nanoparticles into polysulfone. The
surface of the nanoparticle was treated with a silane-based modier to improve its distribution in
the host polymer. Atomic-force microscopy, scanning electron microscopy, Fourier transform
infrared spectroscopy, BrunauerEmmettTeller, transmission electron microscopy, energy-
dispersive x-ray spectroscopy, porosity and contact angle tests were conducted to characterize
the properties of the particles as well as the fabricated nanocomposite membranes. The effects of
the nanoparticle incorporation were evaluated by conducting ultraltration experiments. It was
reported that the membrane pure water ux was increased with increasing NTiO2 loading owing
to the high porosity of the nanoparticles embedded and/or formation of enlarged pores upon
addition of them. The antifouling capacity of the membranes was also tested by ultraltration of
bovine serum albumin fouling solution. It was found that both water ux and antifouling
capacity tended to reach desired level if the NTiO2 added was at optimized loading.

Keywords: nanocomposite membrane, nanoporous titanium dioxide, antifouling, ultraltration


membrane
(Some gures may appear in colour only in the online journal)

1. Introduction particles are prevented. In other words, UF works based on


size exclusion mechanism [1, 2]. UF has been used widely in
Ultraltration (UF) is a technique used for separation of many areas including dairy, oil, paper and pulp industries. In
macromolecules and suspended solids from liquids. Small milk processing plants, for example, UF membranes are used
molecules pass through the membrane together with the sol- for whey concentration and milk dehydration. However, in
vent liquid while the passage of macromolecules and/or solid the food industry, they are used for recovering proteins and

0957-4484/16/415706+11$33.00 1 2016 IOP Publishing Ltd Printed in the UK


Nanotechnology 27 (2016) 415706 H C Bidsorkhi et al

carbohydrates from palm oil mill efuent [3, 4]. In drinking mechanical properties and thermal stability. Its presence in
water plants, UF membranes are replacing conventional the membranes changes pore size and pore size distribution
technologies such as sand ltration, since it is able to remove [24]. It could also improve membrane hydrophilicity, per-
bacteria and viruses to deliver clean drinkable water even in meability and solute rejection [25]. Addition of TiO2 is also
the municipal scale [5]. In many petrochemical and steel- reported to play a role in decreasing fouling tendency of the
making plants, large quantities of oily wastewater are pro- membranes and guarantees stable long-term performance in
duced and their recovery is vital. Cleansing by UF mem- industrial plants [26].
branes gives the chance of removing tiny oil droplets of In this research, a spindle-shaped anatase nanoporous
submicron size, whereas such level of purity is not achievable TiO2 (NTiO2) is added to PSF to fabricate novel type of UF
by other conventional techniques like gravity separation and nanocomposite membranes. In comparison with membranes
air oatation [6]. containing spherical non-porous TiO2 particles, higher por-
Immersion precipitation is a technique by which UF osity of the nanoporous particles, which is conrmed by the
membranes are prepared. A polymer solution is cast to form a UF experiments with the bovine serum albumin (BSA)
thin layer which is then transferred to a coagulation bath solution, enhances the ux of the membranes more sig-
immediately or after a delayed time [7]. Polyacrylonitrile, nicantly. In the permeation experiments and antifouling
polyethersulfone, polysulfone (PSF), polyvinylidine uoride tests, effects of the presence of NTiO2 on ux value, rejection
and cellulose acetate are widely used in UF membrane and recovery ratio were evaluated.
manufacturing [8, 9]. It should be noted that most of the
membranes made of the aforementioned materials face foul-
ing problems. Fouling is categorized into reversible fouling 2. Experimental
which can be obviated by membrane cleaning and irreversible
fouling which cannot be prevented. Fouling is caused by 2.1. Materials
different reasons including adsorption of foulants, blocking of
pores and cake formation [10]. Currently, the most simple yet PSF (MW: 65 000 g mol1) was purchased from Shuguang
effective method to reduce membrane fouling is to enhance its Chemical Factory, China. Polyvinylpyrrolidone (PVP, MW:
surface hydrophilicity by blending it with hydrophilic poly- 55 000 g mol1) and n-methyl2-pyrrolidone (NMP, purity:
mers such as polyethylene glycol and polyvinylpyrrolidone 95%) were supplied by Sigma-Aldrich. Nanoporous TiO2 was
(PVP) or grafting its surface with hydrophilic bran- synthesized according to the method of Ye et al [27]. [1-(2-
ches [11, 12]. amino-ethyl)-3-aminopropyl] trimethoxysilane (AAPTS) was
Addition of inorganic nanoparticles is another approach purchased from Merck Co. Bovine serum albumin (BSA,
to overcome membrane shortages including low ux, bio- MW: 66 000 g mol1) from Sigma-Aldrich was used as the
fouling, low hydrophilicity and inferior mechanical properties foulant. Acetic acid (HAc) and tetrabutyl titanate (TBT) were
[13, 14]. Many attempts have been made by introducing purchased from Beijing Chemical Reagent Co. and Beijing
various types of nanoparticles (based on halloysite nanotubes, Great Wall Chemical Reagent Co., respectively.
titania, silver, iron, zirconium, silica and alumina) into poly-
meric matrices to enhance membrane properties such as
2.2. Membrane fabrication
selectivity, permeability, antifouling properties, etc [1518].
Zodrow et al [19] incorporated nanosilver particles into PSF Nanoporous anatase TiO2 particles were obtained through
to improve resistance of the membrane against virus pene- solvothermal reaction of the TBT and HAc solution. Under
tration and biofouling. UF membranes made of such modied continuous agitation, 0.2 ml of TBT was added dropwise to
PSF were used in drinking water purication instruments. 10 ml of HAc. The resultant white suspension was transferred
Silica (SiO2) nanoparticles were also added to the PSF to a 20 ml Teon-sealed stainless-steel autoclave and heated
membrane, which resulted in facile operation and high ther- to 200 C and kept for 24 h. The autoclave was allowed to
mal/chemical resistance [19]. It is proved that these mem- cool to room temperature and the nal product was obtained
branes possessing a hybrid structure are efcient for by centrifugation. The resultant material was washed with
separating oil droplets from oily wastewater. Iron nano- ethanol several times and subsequently dried at 60 C over-
particles on the other hand were considered as potential night. To remove remaining organic compounds, the product
nanollers to develop membranes sensitive to magnetic elds was calcined at 400 C for 30 min [27].
[20]. Beneting from different behavior of a solute/polymer To modify the surface of the synthesized nanoparticles,
pair in a magnetic eld, the membrane performance can be silane-coupling agent (AAPTS) bearing NH2 functional
improved. groups was used. To synthesize modied NTiO2, 1.0 g of
Titanium dioxide (TiO2) is a commonly used nano- nanoparticles was added into 50 ml toluene containing 1.0 g
particle in UF membrane manufacturing [21, 22]. It is a of AAPTS. The mixture was then stirred at 95 C overnight
hydrophilic inorganic nanoparticle with a high level of che- followed by ltration and subsequent washing using toluene,
mical stability, which endows membranes with photocatalysis ethanol, ethanol/water (1:1 v/v) and water. The nal product
features [23]. Furthermore, TiO2 is commercially available was then dried at 100 C in a vacuum oven overnight [28, 29].
and is not very expensive. Usually TiO2 forms strong inter- The silane-modied nanoparticles are named NTiO2 there-
actions with host polymers leading to improvement in after. Dope solution containing 17.5 wt% PSF, 0.5 wt% PVP

2
Nanotechnology 27 (2016) 415706 H C Bidsorkhi et al

and 82 wt% NMP was rst prepared before a pre-determined effective area of 12.57 cm2 was used. At rst, the pure water
amount of NTiO2 (0.5%, 1% and 2% of PSF) was added to was allowed to pass through the membrane for 1 h. Subse-
form a homogenous mixture. The mixture was degassed for quently, the pure water feed was replaced by the BSA solu-
24 h at 25 C to eliminate trapped air bubbles. The obtained tion (100 ppm) which was ltered for 1 h. Finally, pure water
polymer/nanoparticle suspension was cast on a glass plate was used again as the feed during the third hour of the
and rapidly transferred to a water coagulation bath at room experiment. The permeate ux ( J) of the membranes were
temperature. The polymeric lm was peeled off from the glass calculated by:
plate spontaneously upon completion of phase inversion. The J = V AT, (2 )
membranes were stored in a fresh water bath for 24 h to
assure complete removal of the residual solvent. Finally, the where V is the permeate volume, A is the effective area of the
membranes were kept in deionized water prior to their use. membrane and T is the time required to collect V. The solute
rejection was obtained by
2.3. Characterizations R = (1 - Cp Cf ) 100, (3 )
Transmission electron microscopy (TEM model JEM-100 CX where Cp and Cf are the concentrations of BSA in the
II) was applied to observe the nanoporous structure of the permeate and feed streams, respectively, measured by the
inorganic particles. Scanning electron microscopy (Shimadzu UVvis spectroscope (Perkin-Elmer Lambda 25), at the
table top SEM) was used to observe the surface morphology absorption peak of 280 nm.
of the membranes. The membranes were fractured in liquid
nitrogen to examine the cross-sectional morphology of them. 2.5. Antifouling experiments
Both surface and cross-section of the membranes were gold
Flux recovery rate, FRR, was obtained for the membranes
sputtered before being mounted to the SEM equipment.
according to the following equation
Fourier transform infrared spectroscopy (FTIR) spectra were
recorded in the range of 4000400 cm1 using UATR, Per- J
FRR = w2 100, (4 )
kin-Elmer. The tests were done on the NTiO2 nanoparticles, Jw1
PSF and NTiO2PSF nanocomposite membranes. The test
was carried out to evaluate the surface area of unmodied and where Jw1 and Jw2 are pure water ux at the 60 min (end of
modied TiO2 particles. ASAP 2010, Micromeritics, was the rst cycle of the pure water permeation experiment) and
used to perform the test. The surface roughness of the 130 min (beginning of the second cycle of the pure water
membranes was assessed by an qtomic force microscope permeation experiment). The total, Rt, reversible, Rr, and
(NanoSurf Easy Scan). irreversible, Rir, fouling were determined according to the
The crystalline structures of the NTiO2 nanoparticles, following equations
PSF and NTiO2PSF nanocomposite membranes were eval- Rt = (1 - Jp Jw1) 100, (5 )
uated by x-ray diffractometer (D/max-rB 12KW Rigaku). R ir = Rt - Rr , (6 )
The spectra were recorded in a 2 range of 1080 with a
Jw2 - Jp
step size 0.1 and a rate 1 s step1. A goniometer (OCA 15 Rr = 100, (7 )
Plus, Data Physics) was used to measure the contact angle of Jw1
the membranes based on the sessile drop technique. The where Jp is the permeation ux at 120 min (end of the UF
droplets were placed on ve different points of the membrane experiment).
and the average value was reported as the contact angle. After
immersing the membranes in deionized water for a sufcient
amount of time, the water at the membrane surface was 3. Results and discussion
blotted with tissue paper. The wet and dry weights of mem-
brane were measured and the porosity was calculated as fol- Figure 1 shows TEM micrographs of NTiO2. It is obvious that
lows the particles do not have a perfect spherical shape and their
Ww - Wd surfaces resemble a porous structure. Figure 2 shows the
Porosity (%) = , (1 ) BrunauerEmmettTeller (BET) results of NTiO2 nano-
rwater *A*L
particles. The presence of rather uniform nanoporous with an
where Ww, Wd, water, A and L are the weight of the membrane average diameter of 3.9 nm was conrmed by the corresp-
in the wet and dry states, density of water, the membrane onding nitrogen adsorption/desorption measurement. The
surface area and the membrane thickness, respectively. BET data also revealed the high surface area of the NTiO2
compared with the unmodied nanoparticle. The surface areas
for the former and the latter are 112.25 m2 g1 and
2.4. Performance study
50.50 m2 g1, respectively. High surface area of NTiO2 also
The performance of the membranes was evaluated by UF indicates its high porosity which will be discussed in the
experiments using a laboratory-made cross-ow UF cell. The following sections. Nanoporous nanoparticles have signicant
pressure and the feed ow rate were kept constant at 1 bar and advantages over their non-porous or porous counterparts.
400 ml min1, respectively. A disc-like membrane with an High specic surface area is their most important feature as it

3
Nanotechnology 27 (2016) 415706 H C Bidsorkhi et al

Figure 1. TEM micrographs of NTiO2 at different scale bars, (a) 500 nm and (b) 20 nm.

means more interaction sites and better antifouling properties.


They can have high crystalinity and large pore size as well
[30]. Hence, it can be expected that NTiO2 particles could
show a signicant antifouling improvement over non-porous
material.
In gure 3, FTIR spectra of NTiO2, PSF and NTiO2PSF
nanocomposite membrane are displayed. A silane-based
coupling agent was used to reduce surface energy of the
nanoparticles, minimizing their agglomeration in the mem-
brane. It has already been reported that establishment of
physical interactions upon addition of inorganic particles into
polymers could lead to change in the position and intensity of
peaks in FTIR spectrum [31]. In the NTiO2 spectrum, the
peak which appears at wavenumbers around 8301110 cm1
can be attributed to SiO covalent bond while the peak near
2950 cm1 is ascribed to alkyl groups of the modier [32].
Considering PSF and NTiO2PSF spectra, a stronger peak at
Figure 2. The adsorption and desorption prole of NTiO2 around 2980 cm1 is observed in the latter compared with the
nanoparticles for BET measurement. former. Increase in the intensity of this peak can be related to
the presence of NTiO2 in the membrane [33]. These results
show that a strong interaction exists between the host polymer
and NTiO2.
To strongly support the presence of the modier at the
surface of nanoparticles, FTIR spectra of bare TiO2 and
NTiO2 are displayed in inset of gure 3. A new peak arising
at the wavenumbers around 1650 cm1 for NTiO2 is ascribed
to NH covalent bond formed at the surface of the particles
after the silane modication. An extra shoulder in FTIR
spectrum of the NTiO2 at around 920 cm1 signies occur-
rence of condensation reaction between silanol groups and
surface hydroxyl ones [34]. In addition, the appearance of two
peaks at 1154 and 1213 cm1 that is related to SiO and CN
bonds, respectively further supports the successful modica-
tion of nanoparticles by the AAPTS [32].
Figure 4 presents the AFM micrographs of the membrane
while table 1 shows the root average arithmetic roughness
values (Ra) of membrane top surface. As can be seen, increase
in the NTiO2 loading leads to roughness increment. The
Figure 3. FTIR spectra of NTiO2, PSF and NTiO2PSF membrane observation is in good agreement with the ndings reported
(Inset: FTIR spectra of the bare and silane-modied TiO2). elsewhere [35]. Although it is widely reported that the

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Nanotechnology 27 (2016) 415706 H C Bidsorkhi et al

Figure 4. 3D AFM images of the membrane top surface, (A) pure PSF, (B) 0.5% NTiO2PSF, (C) 1% NTiO2PSF and (D) 2% NTiO2PSF.

Table 1. Surface roughness and contact angle of the pure membrane porosity, pore size and pore size distribution. For example,
and nanocomposite membranes. comparing two membranes with a similar hydrophilicity, the
Membrane Roughness, Ra (nm) Contact angle () one which has the higher roughness shows the higher contact
angle [37]. However, the level of improvement varies
PSF 9.4 67.0 depending on the type of TiO2 (nanoporous or non-porous).
0.5% NTiO2PSF 11.1 64.7 As shown in table 1, the contact angle of membrane for 0.5%
1% NTiO2PSF 14.6 59.9
NTiO2PSF, 1% NTiO2PSF and 2% NTiO2PSF are 64.7,
2% NTiO2PSF 22.1 55.7
59.9 and 55.7, respectively, while 83, 79 and 74 were the
contact angle values reported by Zhang et al [38] for similar
PSF composite membranes using non-porous TiO2 particles.
increase in surface roughness could reduce membrane anti- This signicant difference in water contact angles can be
fouling properties following an increase in adsorption sites attributed to the difference on porosity of the nanoparticles
[36, 37], the introduction of hydrophilic NTiO2 into PSF used, i.e. one is nanoporous and the other is non-porous.
membrane on the other hand will improve membrane Nevertheless, we cannot rule out the effect of surface
hydrophilicity and enhance anti-fouling. It seems there is a roughness (based on Wenzel and Cassie effect) that might
competition between roughness and hydrophilicity incre- play partial role in inuencing the contact angle of the
ments upon the addition of the NTiO2. When hydrophilicity membranes incorporated with nanoporous or non-porous
improvement is more signicant, anti-fouling properties particles.
increases, however, they decrease when roughness overcomes According to the procedure mentioned above, calculated
hydrophilicity. The results of FRR that will be presented in porosity values for the neat PSF, 0.5% NTiO2PSF, 1%
following sections can be justied by this hypothesis. NTiO2PSF and 2% NTiO2PSF membranes are 72%, 78%,
Contact angle measurements were also performed to 81% and 87%, respectively. It should be emphasized here that
evaluate the effect of the NTiO2 on the hydrophilicity of the these values denote to the total porosity of the membranes
membranes. The results are presented in table 1. As expected, including bulk porosity and skin layer one. Comparing these
the contact angle decreases (hydrophilicity increases) with an membrane porosity values with the ones reported for mem-
increase of the NTiO2 loading. It should be mentioned that the branes containing non-porous TiO2 particles reveals that
contact angle is dependent not only on the surface hydro- incorporation of the NTiO2 particles increases porosity sig-
philicity but also on various other parameters like roughness, nicantly [39]. Usually, addition of an appropriate amount of

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Nanotechnology 27 (2016) 415706 H C Bidsorkhi et al

XRD and FTIR results show displacement in peak locations,


the presence of physical interactions in the NTiO2PSF
membrane is conrmed.
Figure 6 shows the SEM images of the neat PSF mem-
brane and the membrane incorporated with different loadings
of NTiO2. As can be seen, presence of the pores at the
membranes surface is clearly observed at scale bar of 20 mm.
White spots in the images denote the NTiO2 particles.
Although the surface of the TiO2 particles was modied,
some small aggregates are still observable particularly in the
case where NTiO2 loading was at the highest. The size of the
aggregates increases with an increase in the ller loading. It is
often reported that addition of nanoparticles causes increase in
population of pores at the membrane surface [18].
In gure 7, SEM cross-sectional micrographs of the
membranes are presented. The upper and lower rows show
the low (scale bar: 200 mm) and high magnications (scale
Figure 5. X-ray diffraction (XRD) spectrum of (a) PSF, (b) NTiO2 bar: 50 mm) of the image, respectively. The bright spots in the
and (c) NTiO2PSF. cross-section are the NTiO2 particles. Similar to the surface
images, small aggregates are observable in the 2.0%NTiO2
inorganic nanollers leads to an increase in the population of PSF membrane. It seems that the cross-section consists of
pores and the total porosity of the membranes. Upon three layers, a top skin layer, an intermediate layer of nger-
shrinkage of the polymer after casting the polymer/inorganic like structure and a layer of large macrovoids. As the ller
ller mixture, a mechanical stress is generated between the loading increases, the skin layer becomes thinner, the nger-
polymer and ller, which becomes the driving force for like voids turn into macrovoids, and nally the size of mac-
creation of pores between them. This may occur in the bulk rovoids increases. These results can be explained as follows.
membrane phase as well as at the skin layer. However, it With an increase in the NTiO2 loading, the casting dope
should also be emphasized that a high loading of the nano- becomes more hydrophilic and viscous. The increase in
particles causes creation of large macrovoids and formation of hydrophilicity enhances the solvent (NMP)/nonsolvent
the nanoparticle aggregates at the skin layer as well as in the (water) exchange rate and more nonsolvent is drawn into the
bulk [25]. This phenomenon signicantly deteriorates per- cast lm, whereas viscosity increase slows down the solvent/
formance of the membranes and this is why the concentration nonsolvent exchange. These two opposing effects are super-
of the NTiO2 particles was kept below 2% in this research. imposed in controlling the membrane morphology. At the low
XRD analysis was also carried out to evaluate dispersion NTiO2 loading, the hydrophilicity effect is predominant and
quality and possible interactions of the NTiO2. This inorganic the pore size and porosity increase with an increase in the
nanoparticle has two different structural forms named anatase NTiO2 loading, whereas at higher NTiO2 loading, the visc-
and rutile. Although the chemical structure of both forms is osity effect becomes predominant resulting in smaller pore
similar, their dissimilar crystalline structures result in differ- size and less porosity. It seems the hydrophilicity effect is
ence in angle and intensity of peaks in XRD spectrum. The predominant at the NTiO2 concentration below 2% and the
XRD spectra of PSF, NTiO2 particle and the NTiO2PSF viscosity effect may become observable at the NTiO2 con-
composite membrane are shown in gure 5. PSF shows a centration above 2%. In fact, it has been reported that the
broad peak at 2 of 18 and some other sharp peaks at higher macrovoids disappear at the NTiO2 concentration of 3% [37].
angles which are related to different crystalline structures that Subsequently, the membrane becomes homogeneous and
exist in PSF [40, 41]. Although TiO2 shows three main peaks dense at higher NTiO2 loadings. Finally, the NTiO2 nano-
at 25.32, 37.86 and 48.06, the peaks are ascribed to NTiO2 particles aggregate when their loading level is high and this
crystals with the tetragonal anatase phase [39]. The NTiO2 causes the surface pores blocking and membrane ux
PSF membrane shows a broad peak at around 18, a strong decreasing. Thus, a great attention should be paid to the
sharp peak at around 29 and one another peak at 25 which is amount of the incorporated NTiO2.
bolded by an arrow. These peaks and the ones at larger angles The presence of NTiO2 nanoparticles at the surface of the
are all originated from both NTiO2 and PSF. These obser- membrane was examined by performing an energy-dispersive
vations conrm the presence of the NTiO2 in PSF-based x-ray spectroscopy (EDX) test on the 0.5% NTiO2PSF
membrane and verify its interaction with the host polymer. membrane. In gure 8, the peaks at 4.5 and 2.5 KeV are
Other researchers who studied the PSF/TiO2 membrane also attributed to Ti and Si elements, respectively. The presence of
used XRD analysis to evaluate existence of interaction these two important peaks suggest the successful embedment
between the inorganic nanoparticles and the host polymer of NTiO2 in the PSF membrane matrix [33]. Other NTiO2
[40]. The researchers concluded the establishment of physical PSF nanocomposite membranes exhibit similar spectra, but
interactions between TiO2 and PSF by observing some with slight difference in the peaks intensity (results not
changes in the location of the aforementioned peaks. As both shown here).

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Nanotechnology 27 (2016) 415706 H C Bidsorkhi et al

Figure 6. SEM micrographs of the surface morphology of the (a) pure PSF, (b) 0.5% NTiO2PSF, (c) 1% NTiOPSF and (d) 2%
NTiO2PSF.

Figure 7. SEM micrographs of cross section of membranes containing 0.5% NTiO2 (a), (d), 1% NTiO2 (b), (e) and 2% NTiO2 (c), (d).

The pure water uxes of the membranes containing ux decreases with time and the rate of the ux decline
various amounts of the NTiO2 are displayed in gure 9. The depends on the ller loading. The ux of neat PSF and 0.5%
gure shows that the pure water ux increases with an NTiO2PSF membranes decreases only little with time while
increase in the amount of the NTiO2. However, the pure water the decrease is more signicant for 1% NTiO2PSF and 2%

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Nanotechnology 27 (2016) 415706 H C Bidsorkhi et al

Figure 8. EDX spectrum of PSF membrane containing 0.5% NTiO2.

Figure 9. Pure water ux of membranes versus ltration time. Figure 11. Rejection of membranes against BSA foulant at
different time.

NTiO2PSF membranes. As mentioned earlier, the effects of


hydrophilicity and viscosity on the macrovoid formation are
opposite, among which the effect of hydrophilicity is stronger
as the NTiO2 concentration falls behind 2%, resulting in
increase in pore size and porosity. This is the main reason for
the increase in pure water ux with an increase in NTiO2
loading.
The results of the UF experiments with the BSA feed
solution are presented in gures 10 and 11. Similar to pure
water ux, the ux in the presence of foulant increases as the
NTiO2 loading increases, and a more signicant ux reduc-
tion is observed at higher NTiO2 loadings. Especially for 2%
NTiO2PSF membrane, the ux falls behind the ux of 1%
NTiO2PSF membrane after 50 min. With respect to foulant
Figure 10. Permeate ux of the membranes in ltrating fouling rejection, it is found that membrane separation efciency
aqueous solution. tends to decrease with the NTiO2 loading. This is in

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Nanotechnology 27 (2016) 415706 H C Bidsorkhi et al

NTiO2PSF and 2% NTiO2PSF membranes do not fully


regain this ability. In other words, FRR is more pronounced
for the former samples in comparison with the latter ones. The
trend in FRR is shown in table 2 in details. Referring to the
table, FRR increases by addition of 0.5% NTiO2, however, its
further addition causes reduction in FRR. Thus, the addition
of NTiO2 can affect FRR both positively and negatively.
Similar effects were also reported elsewhere [41, 43].
Therefore, it can be said that a small amount of NTiO2
enhances FRR but a large amount of NTiO2 causes the
decrease in FRR as a result of poor particle dispersion in
membrane matrix. In table 2, total, reversible and irreversible
fouling dened by equations (5)(7) are also shown. Severe
irreversible fouling is observed for 1% NTiO2PSF and 2%
Figure 12. Fouling experiments on different membranes. NTiO2PSF and this is the reason why these membranes
cannot recover their pure water ux after being polluted by
Table 2. Flux recovery ratio (FRR), total fouling (Rt), reversible
foulant. Large pores can accommodate the molecules, causing
fouling (Rr) and irreversible fouling (Rir) of various membranes. the pore blocking. A similar explanation was given by other
researchers for the increase of irreversible fouling due to the
Membrane FRR Rt Rr Rir
non-porous TiO2 addition [43].
PSF 95.8 33.3 29.1 4.2
0.5% NTiO2PSF 100.0 33.3 33.3 0.009
1% NTiO2PSF 82.7 60.9 43.6 17.3
4. Conclusions
2% NTiO2PSF 82.7 72.4 55.1 17.3

PSF membranes containing different amounts of NTiO2 (zero,


0.5, 1 and 2 wt%) nanoparticles were prepared by the phase
accordance with other work where the negative effects of inversion method. The amount of the nanoparticle was limited
inorganic nanoparticles loading on the solute rejection were to 2 wt% in order to prevent the formation of the nanoparticle
reported [30]. The BSA foulant separation of the neat PSF aggregates. The nanoporous NTiO2 synthesized by sol-
and 0.5% NTiO2PSF membranes are nearly equal to 100%, vothermal method is very potential to be used as nanoller for
but those of 1% NTiO2PSF and 2% NTiO2PSF are lower the fabrication of UF membrane with high water ux, high
than 100%. This is because of the pore size increases together BSA foulant rejection and near zero irreversible fouling. The
with the enhancement of the macrovoid formation, as men- FTIR and XRD analyses conrmed the formation of strong
tioned when SEM cross-sectional images were discussed. interactions between the silane modied nanoparticles and the
In comparison with the work of Yang et al [25] who used host polymer matrix. The uniform dispersion of the NTiO2
non-porous surfactant-modied TiO2, the membranes pre- observed in both top-surface and cross-sectional SEM images
pared in this work with nanoporous TiO2 showed higher BSA of the membranes conrmed the appropriateness of the silane-
foulant rejections. The BSA foulant rejections of NTiO2 based modier for surface treatment of the nanoparticles.
containing membranes are generally very high. This is Incorporation of the nanoporous particles also resulted in low
because of the negative charge of TiO2 at a pH above 5. Since contact angle and high porosity. The comparison between
foulant is also a negatively charged molecule, it is rejected nanoporous particles and its non-porous counterparts stipu-
from the membrane surface due to the electrostatic repulsive lated the advantages of the former over latter.
forces. In addition, high hydrophilicity of the surface of the
membranes caused by incorporation of the NTiO2 leads to
formation of a water layer on the surface of the membranes. References
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