Desalination 313 (2013) 199–207

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Desalination
journal homepage: www.elsevier.com/locate/desal

Enhanced hydrophilicity and salt rejection study of graphene oxide-polysulfone

mixed matrix membrane
B.M. Ganesh a, Arun M. Isloor a,⁎, A.F. Ismail b
a
Membrane Technology Laboratory, Department of Chemistry, National Institute of Technology, Karnataka, Surathkal, Mangalore 575 025, India
b
Advanced Membrane Science and Technology Centre (AMTEC), Universiti Teknologi Malaysia (UTM), Skudai, Johor Baru, Malaysia

H I G H L I G H T S G R A P H I C A L A B S T R A C T

Graphene oxide (GO) dispersed polysulfone (PSf) mixed matrix membranes were prepared by the wet phase
► Graphene oxide dispersed polysulfone inversion method. Membranes exhibited improved salt rejection after GO doping. Membrane with 2000 ppm
mixed matrix membranes were pre- GO loading has exhibited a maximum of 72% Na2SO4 rejection.
pared.
► Membranes were characterized.
► Membranes exhibited improved salt
rejection after graphene oxide doping.
► Membranes showed increased hydro-
philicity after doping.

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

Article history: Graphene oxide (GO) dispersed polysulfone (PSf) mixed matrix membranes were prepared by wet phase in-
Received 27 October 2012 version method. The morphology of membranes was studied using scanning electron microscope (SEM) im-
Received in revised form 28 November 2012 ages. The variation in hydrophilicity was studied by measuring surface wettability and water swelling
Accepted 29 November 2012
experiments. The performance of membranes in terms of pure water flux and salt rejection was studied.
Available online 28 January 2013
SEM images depict enhanced macrovoids, while the contact angle data reveals that, GO incorporated mem-
Keywords:
brane surface is moderately hydrophilic. Membranes exhibited improved salt rejection after GO doping.
Graphene oxide Membrane with 2000 ppm GO loading has exhibited maximum of 72% Na2SO4 rejection at 4 bar applied
Polysulfone pressure. The salt rejection seems to depend on pH of the feed solution and it has been witnessed that the
Nanofiltration salt rejection showed an increasing trend with increase in the pH.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction
In recent times, considerable efforts have been put towards ob-
taining fresh water from abundantly available saline sea water. In
⁎ Corresponding author. Fax: +91 824 2474033.
E-mail address: isloor@yahoo.com (A.M. Isloor).
this direction the pressure driven membrane filtration has gained sig-
nificant ground [1]. This is majorly due to two factors, one is because
of its ease of operation and more importantly these filtration process-
es are cost effective compared to all other conventional filtration
techniques. For membrane filtration, polysulfone (PSf) based mem-
branes are used most extensively because of its excellent heat resis-
tance, chemical compatibility and resistance over wide range of pH

0011-9164/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.desal.2012.11.037
200 B.M. Ganesh et al. / Desalination 313 (2013) 199–207
[2]. The major drawback of these PSf membranes is that, they are hy-
drophobic in nature, whereas the desalination membranes demand
appreciable hydrophilicity in order to cope up with productivity is-
sues. Also in general membranes suffer from fouling and hence lead
to low membrane life time. The low permeability and fouling are
mainly due to low surface hydrophilicity and low porosity. So, all
over the globe, desalination researchers are looking for a membrane
with finely-balanced characteristics.
The most widely employed method for increasing the surface hydro-
philicity is to blend the PSf with some surface modifier. Mahesh et al.
showed technique of increasing hydrophilicity by blending PSf with
hydrolyzed poly isobutylene-alt-maleic anhydride and witnessed
enhanced performance for the same [3]. Enhanced hydrophilicity as
well as improved salt rejection was achieved through PSf blend mem-
brane with modified poly isobutylene-alt-maleic anhydride [4]. In this
direction, Vatanpour et al. and Evrim et al. were successful in increasing
hydrophilicity and antifouling property of the membrane by preparing
polyethersulfone (PES) composite membrane with functionalized
multi walled carbon nanotubes (MWCNT) [5,6]. Choi et al. prepared
MWCNT mixed matrix membrane and witnessed enhanced hydrophi-
licity as well as the dependence of pore size on the content of
MWCNT [7]. Also chitosan modified carbon nanotubes (CNTs) were
used as a performance modifier in mixed matrix polyimide composite
membranes [8]. From these works it can be understood that, further
modification of existing membranes is required in order to improve
their performance. Keeping this in view, in the present work graphene
oxide (GO) is being utilized as a performance modifier for the prepara-
tion of PSf based mixed matrix membrane.
GO is gaining much more interest in the field of material research
due to its high surface area, outstanding electron transport and
mechanical properties. These atomically thin carbon sheets when in-
corporated appropriately into polymer matrix, can significantly im-
prove physical properties of the host polymers at extremely low
dope concentration. The objective behind choosing GO as an additive
lies in its hydrophilic and pH sensitive behavior. Also it has been stud-
ied and proved that GO can induce surface negative charge. It is also
demonstrated that GO exhibits this property of negative surface
charge throughout the entire pH range [9]. The polymer composite
of GO is found to enhance the mechanical strength of the host poly-
mer. It has also been studied that, incorporation of GO or graphene
into polymer mixed matrix membranes, can appreciably increase
the rejection of gas like nitrogen and oxygen [10–13]. Due to different
types of hydrophilic functional groups present on the surface of GO, it
can take up water very easily and it has also been well understood
that the water uptake increases as the degree of oxidation increases
[14]. Keeping these characteristic features of GO in view, present
investigation has been designed.
2. Experimental
2.1. Materials
Natural graphite was procured from Graphite India. PSf with
Mw-35000 was obtained from Sigma-Aldrich Co Germany. N-methyl-
2-pyrrolidone (NMP) was obtained from Merck India and was used
without purification. Analytical grade H2SO4 (purity 98%), KMnO4
(purity 99%) and H2O2 (30% aqueous solution) were used as received.
2.2. Preparation of GO
There are many methods in practice for the preparation of GO
[15–18]. Initially it has been prepared by oxidation of natural graphite
using NaClO3 as an oxidizing agent, which is widely known as
Brodie's method [19]. In the present work, GO is being prepared by
the oxidation of graphite using KMnO4 as an oxidizing agent.
100 mL of H2SO4 and 1 g of graphite was placed in a round bottomed
flask and was cooled to 0 °C. Then to this suspension, 8 g of KMnO4
was added slowly, while maintaining the temperature below 20 °C
throughout the addition. After the completion of KMnO4 addition,
the temperature of reaction mixture was slowly raised to 30–40 °C
and was kept at that temperature for 30 min. This was followed by
slow addition of 200 mL of water to the reaction mixture. At this
stage the temperature was raised to 90–100 °C and the formation of
brownish color suspension was noticed and the mixture was
maintained at this temperature for 15–20 min. Then to this suspen-
sion, 30 mL of hydrogen peroxide was poured and change in color
of the suspension from brown to yellowish brown was observed.
The reaction mixture was filtered and the residue was washed with
3% HCl. Further this residue was dispersed in water and by centrifuga-
tion, cleaner residue was separated. This oxidized material is then
ultrasonicated in water to get fully exfoliated graphene oxide. After
drying the residue in air, it was used for further characterization
and membrane preparation.
2.3. Characterization of GO
Transmission electron microscope (TEM) image of GO was re-
corded on PHILIPS-CM200 Operating at 20–200 kv with 2.4 A° resolu-
tion. XRD measurements were done using JEOL X-ray diffractometer
with a Cu target at a scanning rate of 2°/min with a step size of
0.02°. Solid state CP-MAS 13C NMR was recorded using BRUKER
make DSX-300 solid state NMR spectrometer with 7 K magic
angle spinning. The NMR delta values are referenced against TMS
(δ = 0 ppm for 13C). IR spectra were recorded on Thermo-AVATAR
ATRIR instrument working with OMNIC version 7.3 processing soft-
ware. Neat samples were introduced onto ATR crystal and percent
transmittance between 400 cm −1 and 4000 cm −1 was measured.
Thermo gravimetric analysis of GO was carried out on SII EXSTAR
6000 series TG/DTA 6300 thermal analyzer. The sample was placed
in platinum pan and the thermogram was recorded between 25 °C
and 800 °C at a heating rate of 10 °C/min, under N2 atmosphere
with a flow rate of 10 mL/min.
2.4. Fabrication of PSf/GO mixed matrix flat sheet membranes
The PSf/GO mixed matrix membranes were prepared by phase in-
version method [20,21]. 25 wt.% PSf solution was prepared by dis-
solving required amount of PSf in NMP solvent. This mixture was
stirred for 24 h at 60 °C to get a homogeneous polymer solution. To
this polymer solution desired amount (1000 ppm and 2000 ppm) of
GO dispersed in NMP solvent was added. Then the solution was
stirred for 24 h to obtain a uniform dispersion of GO in casting solu-
tion. The casting solution temperature was maintained at 60 °C. This
casting solution was then deposited onto a clean glass plate pasted
with adhesive tape on both sides of the plate, and then the solution
was cast using a Doctor's knife. Glass plate was allowed at room tem-
perature for 30 s and then immersed into non-solvent (water) bath.
Glass plate was allowed to stay in the non-solvent bath, until
complete phase inversion was ensured after which membrane got
separated from glass plate. The membrane was peeled, washed thor-
oughly with water to remove any residual solvent in the membrane.
The clean membrane was then stored in slightly chlorinated distilled
water and used for further characterization.
2.5. Characterization of flat sheet composite membranes
To understand the distribution of GO on the membrane surface,
the prepared membranes were characterized by ATR-IR and powder
XRD. The cross sectional morphology of these mixed matrix mem-
branes was studied using SEM images. The effect of GO loading on
surface roughness was studied by analyzing the membrane surface
topology using AFM technique. The surface hydrophilic behavior of
 B.M. Ganesh et al. / Desalination 313 (2013) 199–207
the membrane was tested using water contact angle measurements
whereas bulk hydrophilicity was measured by water uptake study.
The procedure for water uptake study was followed as reported else-
where [4] (presented in supporting information). Water uptake was
calculated using the following equation,
W w −W d
Water uptake ð% Þ ¼  100
Wd
where Ww and Wd are wet and dry weight of membrane samples.
In order to understand the behavior of GO-functional groups
which are present on the membrane surface, the effect of pH on
water uptake was also studied.
2.6. Performance study of the membranes
The performance of the membrane was studied by checking its
pure water flux to understand the water transport behavior of the
membrane. Then these membranes were subjected to salt rejection
study using 1000 ppm NaCl and Na2SO4 solutions. The effect of pH
on solute rejection was also studied. All permeation experiments
were carried out in a dead end flow cell using circular membranes
of 19.6 cm2 effective area available for filtration. External pressure
was applied using nitrogen cylinder capable of producing up to 12 bar
pressure. The solute rejection percentage was calculated using the
following equation,
! The GO sample was subjected to FESEM and TEM analysis. Oxi-
Cp
Salt rejectionð% Þ ¼ 1−  100
Cf
where Cp and Cf are concentration of permeate and feed solution
respectively.
3. Results and discussion
3.1. Characterization of GO
In order to understand the structure of GO (Fig. 1S) (see supporting
information for representative chemical structure of GO), it has been
characterized by infrared spectrum, solid state 13C NMR, FESEM, TEM,
XRD and TGA. Fig. 1 displays the stacked IR spectra of graphite and
GO. IR spectrum of GO demonstrates the presence of many functionali-
ties on the graphite sheet after oxidation. IR assignments are tabulated
in Table 1S (see supporting information). Here one can observe the
broad IR band from around 2400 cm−1 to 3800 cm−1. This can be at-
tributed to O\H stretching of surface functional groups and also due
Fig. 1. Stacked IR spectrum of graphite and GO.
201
to water occluded/adsorbed in GO layers. The presence of more than
one O\H stretch suggests that GO contains O\H groups of different
types. O\H may be present in the form of tertiary alcohol, phenolic,
enolic and also as COOH. The band at 1713 cm−1 is due to C_O
stretching of COOH group. The peak at around 1619 cm−1 has been
assigned to cyclic ether (epoxide) linkage as well as for bending vibra-
tion of H2O molecule present in GO matrix [14]. Whereas, IR spectrum
of graphite is featureless and from this one can conclude that graphite
is effectively being oxidized to GO.
Presence of these functional groups has been evidenced further by
NMR. The solid state 13C CP-MAS NMR spectrum was recorded to un-
derstand the carbon skeletal structure of GO. Fig. 2 shows the typical
13
C spectrum of GO which has characteristic peaks at 59.5, 68.6, 129.3
and 160.5 ppm. Peak at 59.5 ppm is assigned to carbon attached to ep-
oxide group. Signal at 68.6 ppm confirms the presence of C\OH group.
Peaks at 129.3 and 160.5 ppm are assigned to the carbon atoms of con-
jugated double bonds and carbonyl carbon respectively [22].
TGA for GO has been recorded and Fig. 3 displays the TGA graph of
GO. The weight loss (mg) during the heat treatment is shown on the
left axis along with the derivative weight loss (mg) per degree centi-
grade on the right hand axis of the plot. From the derivative graph, it
is clear that the thermogram contains 4 peaks at 61.6 °C, 231.27 °C,
269.5 °C, and 651.4 °C. First peak at 61.6 °C is due to evaporation of
water present in the GO matrix. Next two peaks arise due to dissoci-
ation of functional groups present on the graphite skeletal [23]. Final
peak is the result of sublimation of carbon backbone.
dized graphite generally exists in different folding forms. This can
be observed in the FESEM image (Fig. 4 (A)). Fig. 4 (B) shows the
TEM image of GO. Graphite appears as few micrometers sized stacked
graphene sheets, in TEM image it looks like an agglomeration of car-
bon sheets. But, here from TEM image it can be observed that GO
showed different microstructure with nanometer layer thickness
with folding morphology. It's well-known that graphite exists as
thick, closely packed graphene layers. Once it gets oxidized, the mor-
phology will change drastically, and the thickness of graphene sheets
drops considerably to nanometer level. They lose their flat nature and
display some sort of folding morphology on their surface and at the
edges. The graphene sheet folding can easily be observed from the
portion indicated by arrow mark, and also the portion showed within
a box represents a single sheet of graphene oxide. This type of mor-
phology of GO was reported earlier by Tama'S et al. [14]. So, the ob-
served results are in accordance with earlier reports.
Further GO was characterized by powder XRD. The XRD pattern is
as shown in Fig. 5. GO exhibits a prominent peak at around 10.9°,
which is the characteristic peak corresponding to GO. Disappearance
202 B.M. Ganesh et al. / Desalination 313 (2013) 199–207

13
Fig. 2. Solid state C CPMAS NMR spectrum of GO at 7 K magic angle spinning.

of peak at 26.2° which corresponds to graphite (inside figure) clearly 3.2.2. Powder XRD analysis of membranes
confirms the formation of GO [24]. Also from the figure, a broad peak The powder XRD pattern of pristine PSf as well as mixed matrix
can be observed which may be due to unoxidized graphite present in membranes was recorded (Fig 2S see supporting information). From
the sample. the graph, it can be observed that XRD plots of membranes showed

3.2. Characterization of membranes

3.2.1. IR studies of composite membranes

Once the mixed matrix membranes were completely air dried,
the IR spectra were recorded. From the spectra (Fig. 6) it can be ob-
served that, as the GO loading increases, the peak intensity at
3425 cm − 1, 1728 cm − 1 and 1680 cm − 1 also increases. As it was
well understood from the IR spectrum of GO that, these are charac-
teristic peaks of GO, it confirms the dispersion of GO in polysulfone
matrix. Apart from this, characteristic peaks of PSf were also ob-
served. Peak at around 1295 cm − 1 is arising due to O_S_O asym-
metric stretching, where as the symmetric stretching of O_S_O
giving a band at around 1150 cm − 1. Band at around 1240 cm − 1
and 1040 cm − 1 are characteristic peaks corresponding to asymmet-
ric and symmetric stretching vibrations of C\O\C group. Also peaks
between 2900 cm − 1 and 3100 cm − 1 correspond to aromatic and al-
iphatic C\H stretching vibrations.

Fig. 3. Thermogravimetric curve of GO under N2 atmosphere (10 mL/min) at a heating

rate of 10 °C/min. Fig. 4. (A) FESEM image of agglomerate of GO, and (B) TEM image of GO nano-sheets.
 B.M. Ganesh et al. / Desalination 313 (2013) 199–207
Fig. 5. Powder XRD of GO at a scanning rate of 2°/min with 0.02° step size (inside figure
is powder XRD of graphite).
a characteristic peak of GO at around 2 theta value of 11°. Whereas
the XRD pattern of PSf exhibits a broad peak centered at around
18°. The presence of a peak at 11° in mixed matrix membranes con-
firms the GO dispersion all along the membrane surface. This obser-
vation emphasizes on the formation process of membrane, wherein
hydrophilic GO migrates towards the membrane surface during the
phase inversion process (which will be discussed in detail in
Sections 3.2.3 and 3.2.4).
3.2.3. Morphological analysis
The cross sectional SEM images of prepared membranes were
recorded and shown in Fig. 7. PSf membrane exhibited characteristic
asymmetric structure of dense top layer followed by macro-voids. GO
doped PSf membranes demonstrated (Fig. 7) noticeable changes in
both top layer and sub layer. The macro-void structure was drastically
altered by the addition of GO to polymer matrix. A possible explanation
for this can be given on the basis of the hydrophilic nature of GO. The
hydrophilic nature of GO is responsible for the fast exchange of solvent
and non-solvent during the phase inversion process which leads to
extended porosity as well as changes in the macro-voids structure.
The digital photo images of membrane top and bottom layer is
shown in Fig. 3S (see supporting information). It has been observed
that the color of the top layer (exposed towards the water) is
darker than that of the bottom layer. Vatanpour et al. reported the
similar type of observation for functionalized carbon nano-tube and
polyethersulfone membranes [5]. As it is depicted in an illustrative
diagram showcasing behavior of GO during membrane formation
Fig. 6. Stacked ATR-IR spectra of PSf/GO mixed matrix membranes.
203
(Fig. 8), the movement of GO nanolayers towards top layer makes
the top layer darker.
This can be justified by the fact that, as GO is hydrophilic in nature,
it exhibits higher affinity towards water. As a result, during phase
separation process, hydrophilic GO move towards top layer. This is
well supported by IR data which had demonstrated a broad charac-
teristic stretching band of hydrogen bonding at around 3400 cm −1.
Powder XRD pattern of membranes has also revealed the presence
of GO on the membrane surface. Also this fact was well supported
by contact angle results wherein the water contact angle has shown
decreasing trend with increase in GO doping.
Also membranes were examined for their surface roughness using
AFM measurements. The AFM images of mixed matrix membranes
are as shown in Fig. 9. From the topographical image it can be under-
stood that as the GO loading increased, the surface roughness also in-
creased. This may be due to the fast exchange of solvent and
non-solvent occurring during the phase inversion process because
of the hydrophilic nature of GO [7,25]. The fast exchange of solvents
may result in the formation of spheres or nodules of polymer, as a re-
sult of which the membrane surface becomes rougher and also it may
increase the porosity as well.
3.2.4. Water contact angle of the membranes
The hydrophilicity of the membrane surface can be understood by
water contact angle measurement. Water contact angle was mea-
sured by the sessile drop method [26]. A decreasing trend of contact
angle was observed as the GO loading was increased in polymer ma-
trix (Fig. 10). Lower contact angle leads to the conclusion that, the
membrane surface is more hydrophilic in nature. Pristine PSf mem-
brane had shown highest water contact angle of 71°, whereas
1000 ppm and 2000 ppm GO doped membranes possessed water
contact angle of 65° and 53° respectively. This indicates that the sur-
faces of GO doped membranes are relatively more hydrophilic in
nature. This behavior can be explained by the mechanism of action in-
volved during the phase inversion process. During membrane forma-
tion, the hydrophilic GO migrates towards the top surface of the
membrane as the top layer is more exposed to water (non-solvent).
This is also clear from the IR spectra of the membranes which con-
firmed the presence of hydrogen bonded \OH group. Also the digital
surface images display dark color of the top surface in comparison to
the bottom surface. This clearly indicates the migration of GO to the
top surface. Hence substantiates the hydrophilic nature of the mem-
brane surface.
3.2.5. Water uptake of the membranes
One more conclusive study to understand the hydrophilic proper-
ty of the membrane is water uptake measurement. The water uptake
204 B.M. Ganesh et al. / Desalination 313 (2013) 199–207

Fig. 7. Cross sectional SEM images of pristine PSf and PSf/GO mixed matrix membranes.

of the membrane mainly depends on two factors, firstly on the num- approximated to unity. Qualitatively the FH interaction parameter
ber of hydrophilic sites present in membrane matrix. Secondly, on the represents the affinity of polymer towards solvent. Lower the value
membrane morphology, i.e. presence of macrovoids in the polymeric of χ higher will be the affinity of polymer towards solvent and thus
sub-layer. It can be noted from water uptake results as presented in higher sorption of solvent. By above approximation of unit activity
Fig. 11, that the liquid uptake increases as the GO doping increased of pure solvent, Eq. (1) reduces to,
in the polymer matrix. This is the direct indication of increase in hy-
drophilic sites in polymer matrix. The affinity of membrane towards lna ¼ lnφ þ ð1−φÞ þ χ ð1−φÞ ¼ 0:
2
ð2Þ
liquid can be understood by the theoretical model like Flory–Huggins
(FH) model [27,28]. This model makes use of simple lattice concept to
From Eq. (2), one can find χ.
explain the sorption behavior of liquid in a polymer matrix. This is ap-
plicable to both polar and non-polar solvents. The FH-model deals
with the parameters like FH interaction parameter (χ) deduced by lnφ þ ð1−φÞ
χ¼− ð3Þ
following Eq. (1). ð1−φÞ2

lna ¼ lnφ þ ð1−φÞ þ χ ð1−φÞ

2
ð1Þ The volume fraction φ can be found out by using following formula.

where a and φ are activity and volume fraction of solvent (water). liquid volume
φ¼ ð4Þ
Here for qualitative purpose, the activity of pure solvent will be liquid volume−polymer volume

Fig. 8. Schematic illustration of the behavior of GO during membrane formation.

 B.M. Ganesh et al. / Desalination 313 (2013) 199–207 205

Fig. 9. AFM images of PSf/GO mixed matrix membranes.

These volume terms can be calculated using wet and dry weight of phenomenon. GO has different functional groups attached to its sur-
membrane and density of membrane and solvent used for the study. face which are responsible for surface charge and eventually imparts
Then Eq. (4) can be written as follows. surface charge to membrane. The reaction at GO surface can be sum-
marized as follows.

i. The dissociation of carboxylic group attached to graphitic back

ðmw −md =ρs Þ
φ¼ ð5Þ bone.
ðmw −md =ρs Þ−md =ρm

where mw and md are masses of wet and dry membrane.

ρs and ρm are densities of solvent and membrane respectively.
Table 1 showcases the volume fraction (φ) as well as the FH inter-
action parameter (χ) for pristine and GO doped PSF membranes.
From the values for FH interaction parameter of membranes, it can
be noticed that pristine PSF membrane has the highest value whereas ii. Dissociation of phenolic groups.
2000 ppm GO doped membrane bear least value of 0.22. So with this,
it can be concluded that the affinity of the membrane towards water
increases as the GO doping increases. This is quite obvious that as GO
contains hydrophilic sites in it, which facilitates the uptake of solvent
(water) to membrane matrix. Also it has been observed from SEM
images that the GO doping has resulted in increased macrovoids in
membrane sub layers. Due to this, membrane can accommodate
more solvent molecules and thus increases the overall uptake capac- These are the two major reactions which are responsible for the
ity. The water uptake study was also subjected to pH variations. The production of surface charge. It can be realized from the above fact
observation is plotted in Fig. 11. As it can be seen from the plot, the that, they produce negatively charged ions which interact with
water uptake increases gradually as the pH increases. This is under-
standable observation when GO is involved in the water uptake

Fig. 10. Water contact angle of membranes. Fig. 11. Effect of pH on water uptake.
206 B.M. Ganesh et al. / Desalination 313 (2013) 199–207

Table 1
Volume fraction, and FH interaction parameter for prepared membranes.

Membrane type φ χ

PSf/GO (1000 ppm) 0.34 0.42

PSf/GO (2000 ppm) 0.47 0.22
Pristine PSf 0.27 0.58

water through ion-dipole interaction that leads to increased water

uptake. Also it has been proved through acid base titration method
that as the pH increases from acidic to basic, the equilibrium reaction
shift towards right and as a result it produces more and more nega-
tively charged ions [7]. This is well understood by the result of
water uptake study which has shown an increasing trend with pH.

3.2.6. Pure water flux and salt rejection of the membranes

Fig. 12 manifests pure water flux of the membrane, wherein one
can observe that, as the GO content increases in the membrane, Fig. 13. Na2SO4 rejection results of prepared membranes using 1000 ppm feed solution.
water flux has also increased. It was witnessed by water uptake
study that the solvent uptake increases with GO doping and the
of GO which were mentioned previously are mainly responsible for
same trend has been observed in the case of water flux too. Incorpora-
this behavior. At acidic pH the ionisable groups dissociate to a lesser
tion of GO into membrane matrix results in more and more hydrophilic
extent or in other words the equilibrium lies towards the left and
sites, which facilitates the sorption of water into the membrane. As
therefore produces lesser cation exchange groups. Also the charge
explained earlier for water uptake behavior, the same explanation will
created by the negatively charged groups is less. As a result of these
justify the water flux character of the membrane. It has been observed
the salt rejection at acidic pH is relatively lesser compared at basic
that the formation of macrovoids increased during the phase inversion
pH. One more important observation is that membrane had shown
process because of GO doping. This increased macrovoids is also respon-
relatively stable rejection at all pH values; this indicates that the pre-
sible for the observed increase in water flux. Also this indicated the
pared membranes were stable in the entire pH range. This is one of
increased porosity of membranes after the incorporation of GO.
the major advantages of using PSf as membrane material.
These membranes were scrutinized for salt rejection studies. Salt
rejection was carried out by checking the rejection of 1000 ppm
4. Conclusions
Na2SO4 and NaCl solutions at different applied pressure (Figs. 13
and 14). Also the rejection test was carried out at different pH to un-
Graphite was oxidized to graphite oxide (GO) using KMnO4 in
derstand the charged behavior of the membranes. It can be observed
order to introduce hydrophilic functional groups onto its surface.
from Fig. 14 that the solute rejection was increased with GO doping.
Thus prepared GO was impregnated into polysulfone (PSf) matrix to
Membrane with 2000 ppm GO loading has shown maximum rejec-
prepare PSf/GO mixed matrix membranes. The GO doping into poly-
tion of 72% for Na2SO4 at 4 bar pressure. The rejection shows slightly
mer matrix has resulted in enhanced hydrophilicity, water flux, and
decreasing trend with applied pressure. But it has been observed that
salt rejection property of the membrane. It has been observed that
the decrease in rejection is not severe but definite. It shows that the
GO plays major role in modification of membrane morphology. As it
prepared membranes are mechanically strong enough to withstand
is evident from SEM cross sectional images that, the doping of GO
operating pressure.
has caused significant changes in macrovoids in the sub layer of the
As observed from the water uptake study, pH of feed solution will
membrane. 2000 ppm GO doped membrane has exhibited maximum
play a definite role over deciding the salt rejection behavior of the
salt rejection of 72% for 1000 ppm Na2SO4 solution at 4 bar applied
membrane. The effect of pH on solute rejection was studied using dif-
pressure. It has also been observed that the pH of feed solution has
ferent pH solutions. At acidic pH, the rejection was slightly less in
its influence on salt rejection performance of the membrane. At
comparison with rejection at basic pH (Fig. 15). The surface reactions

Fig. 12. Pure water flux of the membrane at different applied pressure. Fig. 14. NaCl rejection results of prepared membranes using 1000 ppm feed solution.
 B.M. Ganesh et al. / Desalination 313 (2013) 199–207
Fig. 15. Effect of pH on the rejection of 1000 ppm Na2SO4 feed solution at 4 bar applied
pressure.
higher pH, membrane had shown increased salt rejection. This im-
plies that the membrane surface is negatively charged. This negative
charge is imparted by ionisable functional groups present on GO sur-
face. Dependence of rejection and membrane water flux on GO load-
ing once again confirms the charged behavior of the membrane.
Acknowledgment
AMI thanks the Department of Atomic Energy, Board for Research
in Nuclear Sciences—Government of India for the financial support
and ‘Young Scientist’ award. AMI also thanks, Vision Group on Science
& Technology, Government of Karnataka, India for the ‘Best research
paper award’.
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://
dx.doi.org/10.1016/j.desal.2012.11.037.
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