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Effect of PVP Molecular Weights on the Properties of

PVDF-TiO2 Composite Membrane for Oily Wastewater
Treatment Process
ab

ab

ab

ac

C. S. Ong , W. J. Lau , P. S. Goh , B. C. Ng , T. Matsuura

& A. F. Ismail

ab

Advanced Membrane Technology Research Centre (AMTEC), Universiti Teknologi Malaysia,

Johor, Malaysia
b

Faculty of Petroleum and Renewable Energy Engineering, Universiti Teknologi Malaysia,

Johor, Malaysia
c

Industrial Membrane Research Laboratory, Department of Chemical and Biological

Engineering, University of Ottawa, Ottawa, ON, Canada
Accepted author version posted online: 28 Jul 2014.Published online: 30 Sep 2014.

To cite this article: C. S. Ong, W. J. Lau, P. S. Goh, B. C. Ng, T. Matsuura & A. F. Ismail (2014) Effect of PVP Molecular
Weights on the Properties of PVDF-TiO2 Composite Membrane for Oily Wastewater Treatment Process, Separation Science and
Technology, 49:15, 2303-2314, DOI: 10.1080/01496395.2014.928323
To link to this article: http://dx.doi.org/10.1080/01496395.2014.928323

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Separation Science and Technology, 49: 23032314, 2014

Copyright Taylor & Francis Group, LLC
ISSN: 0149-6395 print / 1520-5754 online
DOI: 10.1080/01496395.2014.928323

Effect of PVP Molecular Weights on the Properties of PVDF-TiO2

Composite Membrane for Oily Wastewater Treatment Process
C. S. Ong,1,2 W. J. Lau,1,2 P. S. Goh,1,2 B. C. Ng,1 T. Matsuura,1,3 and A. F. Ismail1,2
1

Advanced Membrane Technology Research Centre (AMTEC), Universiti Teknologi Malaysia, Johor, Malaysia
Faculty of Petroleum and Renewable Energy Engineering, Universiti Teknologi Malaysia, Johor, Malaysia
3
Industrial Membrane Research Laboratory, Department of Chemical and Biological Engineering, University of Ottawa,
Ottawa, ON, Canada

Downloaded by [Universiti Teknologi Malaysia] at 00:36 03 October 2014

Polyvinylidene fluoride (PVDF) hollow fiber ultrafiltration

membranes consisted of TiO2 and different molecular weight (Mw )
of polyvinylpyrrolidone (PVP) (i.e., 10, 24, 40, and 360 kDa) were
prepared to treat synthesized oily wastewater. The membrane
performances were characterized in terms of pure water flux,
permeate flux, and oil rejection while their morphological properties were studied using SEM, AFM, and tensile tester. Results
show that the PVDF-TiO2 composite membrane prepared from
PVP40k was the best performing membrane owing to its promising water flux (72.2 L/m2 .h) coupled with good rejection of oil
(94%) when tested with 250 ppm oily solution under submerged
condition. It is also found that with increasing PVP Mw , the
membrane tended to exhibit higher PVP and protein rejection,
greater mechanical strength, smaller porosity, and a smoother
surface layer. Regarding the effect of pH, the permeate flux
of the PVDF-PVP40k membrane was reported to increase with
increasing pH from 4 to 7, followed by decrease when the pH
was further increased to 10. Increasing oil concentration in the
feed solution was reported to negatively affect the water flux of
PVDF-PVP40k membrane, owing to the formation of thicker oil
layer on the membrane surface which increased water transport
resistance. A simple backflushing process on the other hand could
retrieve approximately 60% of the membrane original flux without affecting the oil separation efficiency. Based on the findings,
the PVDF-TiO2 membrane prepared from PVP40k can be potentially considered for oily wastewater treatment process due to its
good combination of permeability and selectivity and reasonably
high water recovery rate.
Keywords polyvinylidene fluoride; polyvinylpyrrolidone; ultrafiltration; oily solution; hydrophilicity; submerged membrane;
titanium dioxide

Received 7 January 2014; accepted 22 May 2014.

Address correspondence to W. J. Lau, Advanced Membrane
Technology Research Centre (AMTEC), Universiti Teknologi
Malaysia, Johor, Malaysia. E-mail: lwoeijye@utm.my or lau_
woeijye@yahoo.com
Color versions of one or more of the figures in the article can be
found online at www.tandfonline.com/lsst.

INTRODUCTION
Oily wastewater possesses potential risk to the water environment due to the existence of many hazardous hydrocarbon
mixture, chemical components, and heavy metals. To prevent the severe pollution in water environment, a stringent oil
discharge standard is established in different countries. For
instance, in Malaysia, the effluent discharged from industrial
sectors should comply with the national primary regulatory of
discharged standard as stipulated in the Environmental Quality
Act (EQA), 1974. Figure 1 compares the maximum oil discharged concentration set by different countries. As can be
seen, the maximum oil concentration of effluent discharge is
varied from one country to another and this could be due to
the geographical condition and the characteristics of the original wastewater. Compared to other countries, Malaysia is found
to have much lower tolerance value for the oil discharge limit
concentration, i.e., 10 ppm in comparison to 40 ppm found in
the United States and Russia and 100 ppm in Indonesia, Saudi
Arabia, and Qatar. Thus, more exploration in oily wastewater
treatment is required to meet the stringent local discharged limit
and to deal with increasing global oil demand.
As documented in literature, there are many oil separating
methods reported so far concerning the efficiency of the oil
refinery wastewater treatment process. These include gravity
settling, centrifugation, air flotation, fibrous/packed bed coalescence, and membrane-based technologies (17). However,
the increasing global oil demand has made these treatment processes very challenging. In particular, conventional treatment
methods are mostly useful for free oil solution with oil droplets
size > 150 m or unstable oil-water emulsion with droplet sizes
between 20 and 150 m. In order to separate much smaller oil
droplets from stable oil-water emulsion, membrane technologies are generally considered as attractive technique to substitute the existing conventional treatment. Furthermore, it has
been previously reported that for oil and gas produced treatment
process, membrane technologies require significantly lower
energy consumption and operating cost (i.e., $0.080.34/bbl)
than those of conventional technologies ($0.15/bbl) (8, 9).

2303

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2304

C. S. ONG ET AL.

FIG. 1. Maximum effluent discharge oil concentration for produced water in different countries [26].

The low energy consumption of membrane technologies, in particular ultrafiltration (UF), is mainly attributed to low operating
pressure (0.51 bar) applied throughout the operation period
(1013). Even though the operating pressure of UF is remarkably lower than that of nanofiltration (NF) and reverse osmosis
(RO) membranes, its water permeability achieved is still very
promising for industrial application, i.e., 25350 L/m2 .h.bar
(1013). However, some argued that small contaminants and
stable oil-water emulsion might be difficult to remove using
microporous UF membrane compared to NF and RO membranes. In order to extend the uses of UF membrane on the
separation of stable oil-water emulsion, organic and inorganic
additives were used in this work and added into dope solution
with the aims of producing desired properties of UF membrane for this particular process. A literature search revealed
that polyvinylpyrrolidone (PVP) is favored over other organic
additives, mainly due to its excellent pore forming ability and
wide range of molecular weight (Mw ) (14). Table 1 summarizes
some of the previous studies on the use of PVP as additive to
enhance the water permeability of pristine membranes made of
various polymeric materials (1522). Usually, the enhancement
in membrane water flux upon PVP addition is caused by the
formation of finger-like or sponge-like structure in the membrane sublayer. It has been previously reported by researchers
that the higher the Mw of PVP used, the significant the suppression of macrovoids formation and the denser the skin layer,
which leads to lower water flux (16, 21, 23). Nevertheless,
considering the importance of both thermodynamic and kinetic
effects during the phase inversion process, one should be careful about the concentration and Mw of PVP used, which are
dependent on the polymer and solvent type used for dope
preparation.
To the best of our knowledge, the effect of four types of PVP
with different Mw (i.e., 10, 24, 40, and 360 kDa) on the morphology and performance of polyvinylidene fluoride (PVDF)
membrane incorporated with titanium dioxide (TiO2 ) nanoparticles has not been reported so far. In view of this, an attempt

is made to investigate the effect of a wide range of Mw of

PVP (10360 kDa) as additive on the properties of PVDFTiO2 composite membrane for oily wastewater treatment under
submerged conditions. In the selection of membrane-based
polymer and other additives, PVDF blending with 2 wt% TiO2
was favorable due to its good combination of water flux and
oil rejection as reported in our previous research work (25).
In the present work, the changes in the morphological structures
and separation performances of the PVDF-TiO2 membranes are
further investigated by varying Mw of PVP added. The best
performing membrane is further evaluated for oily wastewater
process by varying the oil concentration and pH value of the
synthesized feed solution. A simple backflushing cleaning process is also performed on the membrane in order to investigate
its flux recovery and oil rejection after the cleaning process.
EXPERIMENTAL
Materials

PVDF (Kynar 760) pellets purchased from Arkema Inc.,

Philadelphia, USA were used as the main membrane forming material. N,N-dimethylacetamide (DMAc) (Merck, > 99%)
was used as solvent to dissolve polymer without further purification. Polyvinylpyrrolidone (PVP) (10, 24, 40, and 360 kDa)
purchased from Sigma Aldrich and titanium dioxide (TiO2 )
(Degussa P25, average particle size 21 nm) from Evonik
were used as additives to enhance PVDF membrane properties. Bovine serum albumin (BSA, 67 kDa), egg albumin (EA,
43 kDa), and trypsin (23 kDa) were purchased from Sigma
Aldrich. The cutting oil obtained from Ridge Tool Company,
Ohio, USA was used to synthesize oily solution of different oil
concentrations.
Preparation of Membrane and Membrane Module
18 wt% of PVDF was added into pre-weighed DMAc solvent after being dried for 24 h in oven at 50 C. The solution
was then mechanically stirred at 600 rpm until all the polymeric

2305

EFFECT OF PVP MOLECULAR WEIGHTS FOR OILY WASTEWATER TREATMENT PROCESS

TABLE 1
Overview on the previous studies on the effect of different Mw of PVP on membrane properties

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Reference

MW of PVP
(kDa)

Polymer

Solvent

Jung et al. (17)

10-360

PAN

DMSO

Chakrabarty et al.
(16)

24-360

PSf

NMP,
DMAc

Ochoa et al. (24)

40 and 360

PES

DMF, THF

Zhang et al. (22)

10-1300

PSf

DMAc

Basri et al. (15)

10, 40 and 360

PES

NMP

Lang et al. (19)

10, 24 and 58

PVB

NMP

Sadrzadeh and
Bhattacharjee
(21)

10 and 1300

PES

NMP

Matsuyama et al.
(20)

10-1300

PSf

DMAc

Results on membrane properties

Water flux was improved with addition of
PVP but it was decreased by increasing
Mw of PVP from 10 to 360 kDa.
Increasing Mw of PVP from 24 to 360 kDa
could lead to lower flux due to the
reduction of pore size caused by the
swelling of PVP on the membrane
surface layer.
Permeabilities were increased by adding
PVP40 and 360 kDa into PES dope
solution.
Both the porosity and pure water flux of
membrane were increased by increasing
the Mw of PVP from 10 to 58 kDa but
both tended to decrease with further
increase in the MW of PVP.
PES membrane became more hydrophilic
but the pore size and porosity were not
significantly affected upon PVP addition.
The size and number of membrane pores
decreased with increasing Mw of PVP.
Applying PVP1300kDa in the PES/NMP
solution could result in formation of
denser membrane skin layer which led to
decrease in water flux.
Addition of PVP with high Mw suppressed
the formation of macrovoids and tended
to increase the sponge layer-like structure
in membrane sublayer.

PAN = Polyacrylonitrile, PSf = Polysulfone, PES = Polyethersulfone, PVB = Polyvinyl butyral.

DMSO = Dimethyl sulfoxide, NMP = N-methyl-2-pyrrolidone, DMAc = Dimethylacetamide, DMF = Dimethylformamide, THF =
Tetrahydrofuran.
a

pellets were completely dissolved. It was followed by the addition of 2wt% of TiO2 nanoparticles and 5 wt% of PVP into the
mixture (see Table 2). The dope solution was then ultrasonicated to remove any air bubbles trapped in the solution prior to
the spinning process. The viscosity of the dope solutions was
measured by a basic viscometer (Model: EW-98965-40, Cole
Parmer).
By using the solutions prepared, PVDF membranes of different properties were fabricated using dry-jet wet spinning
method as described elsewhere (27). The as-spun hollow fibers
were immersed into water bath for 2 days to remove the residual solvent. Prior to air drying, the fibers were post-treated by

TABLE 2
The dope formulation of PVDF-TiO2 hollow fiber
membrane with and without PVP additive
Membrane
PVDF (control)
PVDF-PVP10k
PVDF-PVP24k
PVDF-PVP40k
PVDF-PVP360k

PVDF PVP TiO2 DMAc Viscosity

(wt%) (wt%) (wt%) (wt%) (mPa.s)
18
18
18
18
18

5
5
5
5

2
2
2
2
2

80
75
75
75
75

5,375
10,804
11,986
17,118
27,882

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C. S. ONG ET AL.

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10 wt% glycerol aqueous solution for 1 day to minimize fiber

shrinkage and pore collapse. At last, hollow fibers were dried at
room temperature for 3 days before module fabrication.
A bundle of 60 hollow fibers with the length of approximately 28 cm (total effective membrane area: 607 cm2 ) was
potted into a polyvinyl chloride (PVC) tube using epoxy resin

(E-30CL Loctite Corporation, USA). The membrane module

was then left at room temperature for hardening before its protruding parts were cut and fixed into a PVC adaptor to complete
the module preparation.
Preparation of Synthetic Oily Solution
The synthetic oily solution was prepared by mixing distilled
water with commercial cutting oil (RIDGID Nu-Clear Cutting
Oil, #70835, Ridge Tool Company). The emulsion was prepared by keeping the oil-water mixture in a blender (Model:
BL 310AW, Khind) for 2 min with an agitation speed of 50Hz at
room temperature. The size of oil droplets was measured using
Zetasizer Nano ZS (Malvern Instrument Inc., Southborough,
MA), with a refractive index of 1.47 and 1.333 for the oil
droplets and dispersant (water), respectively. The oil droplet
size distribution of the synthesized solution was in the range
of 0.42.6 m with a mean particle diameter of 1.08 m (
0.16), as shown in Fig. 2.
Filtration Experiment
The separation performance was assessed by placing two Ushaped hollow fiber membrane modules at the bottom of a submerged tank containing approximately 14 L of oily wastewater.
To minimize the fouling effect, a constant air flow rate of
5 L/min generated by an air compressor (Model: 2HP single
cylinder 24L tank, Orimas) was used to generate air bubbles

FIG. 2. Size distributions of oil droplets in synthetic oily solution (oil concentration = 250 ppm).

within the submerged tank through air diffuser installed underneath the membrane modules. Water permeate was produced
using a peristaltic pump (Model: 77200-60, Masterflex L/S,
Cole Parmer) by creating a vacuum condition on the permeate
side. Both the vacuum pressure and pump flow rate were kept
constant at 15 inHg and 15 mL/min, respectively, throughout the experimental period. A 10 mL sample was taken from
the permeate for sample analysis and the remaining permeate was recycled back to the tank. Three measurements were
made for each sample and then the average value was reported
together with its standard deviation (based on 95% confidence
level). The membrane water flux (J) was determined according
to Eq. (1).
J=

Q
At

(1)

where J is the water flux (L/m2 h), Q is the quantity of the permeate (L), A is the effective membrane area (m2 ), and t is the
time (h) to obtain the quantity of Q.
The performance of membranes was evaluated using different feed solutions by changing the oil concentration (250 ppm,
500 ppm, and 1000 ppm) in the feed. The membrane oil
rejection was then calculated using the following equation.


Cp
100
R= 1
CF

(2)

where R is the oil rejection (%), Cp and CF are the concentration

of oil in the permeate (ppm) and the feed (ppm), respectively.
The oil concentration in the permeate and feed was determined using a UV-vis spectrophotometer (Model: DR5000,
Hach) measured at a wavelength of 294 nm at which the maximum absorption occurs. On the other hand, the PVP and
protein rejection of membrane were assessed using a lab-scale
cross-flow permeation system as described elsewhere (28). The
experiment was conducted at 1 bar using feed aqueous solution
containing either 1000 ppm BSA, EA, or trypsin. The protein
concentrations in the feed and permeate were then measured
using an UV-vis spectrophotometer at a wavelength of 280 nm
to determine the membrane rejection efficiency. With respect to
PVP rejection four different Mw of PVP (i.e., 10, 24, 40, and
360 kDa) were prepared in the concentration of 1000 ppm. The
TOC concentrations in the feed and permeate were measured by
a TOC analyzer (Model: TOC-LCPN, Shimadzu) to determine
the membrane rejection of PVP.
In addition, the antifouling property of the resulted membrane was also studied in this work. First, the best performing
membrane with balanced performance of permeability and
selectivity was selected to treat the oily solution for 180 min.
After 180 min of experimental run, the feed solution was
replaced with deionized water and the membrane was cleaned
by reversing the direction of the permeate flow for 60 min (also
known as backflushing). Bubbling of air controlled at flow rate

EFFECT OF PVP MOLECULAR WEIGHTS FOR OILY WASTEWATER TREATMENT PROCESS

of 5 L/min was also employed to assist the cleaning process by

removing the oil droplets attached on the membrane surface.

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Membrane Characterization
Contact Angle Goniometer
The contact angle of membranes was determined by the sessile drop technique using a contact angle goniometer (Model:
OCA 15EC, Dataphysics) with deionized water as the liquid.
At least 10 locations were arbitrarily chosen on the membrane
surface in order to yield an average value.
Scanning Electron Microscope (SEM)
The outer surface and cross-sectional morphology of membranes was observed by tabletop SEM (Model: TM 3000,
Hitachi). Prior to the analysis, the hollow fiber was immersed
into liquid nitrogen for a few minutes followed by freezefracturing to obtain a perfect cut structure. The fiber was then
placed onto a carbon-tape aluminum holder and coated with
platinum under vacuum.
Atomic Force Microscope (AFM)
The membrane surface roughness and mean pore sizes were
investigated by AFM (Model: SPA-300HV, Seiko). A small
piece of fiber was cut and adhered on a 1 cm2 square paper
card using double-sided adhesive tape. The membrane surface
was scanned in the size of 5 m 5 m. The surface roughness of the membrane was expressed in terms of mean surface
roughness (Ra ). The pore size on the membrane outer surface was measured by visual inspection on the obtained line
profiles from AFM images of the same membrane at different areas. To obtain the pore size, cross-sectional line profiles
were selected to traverse the micron scan surface areas of the
AFM images. The pore diameter was measured by inspecting
line profiles of different high peaks and low valleys on the
same AFM images. The pore sizes were reported based on the
average of 60 measurements.
In order to investigate the pore size distribution, 60 dark
spots from the AFM images are measured and a graph was plotted according to the method described by Khayet et al. (29).
Based on this method, the measured pore sizes are arranged in
an ascending order. Median ranks are calculated using Eq. (3).

Median or 50 % rank =


j 0.3
100%
n + 0.4

(3)

where j is the order number of the pores when arranged in

ascending order and n is the total number of pores measured.
If pore sizes have log-normal distribution, the median rank
versus ascending pore size would be a straight line on the
log-normal plot. From the graph, the mean pore size (p ) and
geometric standard deviation (p ) can be determined. The mean
pore size will correspond to 50% of cumulative number of pores
and the geometric standard deviation can be calculated from the

2307

ratio of 84.13% of cumulative number of pores to that of 50%.

From the mean pore sizes and geometric standard deviation, the
pore size distribution can be determined using Eq. (4).
 
2
ln dp ln p
df (dp )
1
exp
=
2

d(dp )
dp ln p (2)1/2
2 ln p

(4)

where dp is the membrane pore size (nm), p is the geometric

standard deviation, and p is the mean pore size (nm).
Mechanical Tensile Tester
The fiber tensile test was performed at room temperature
on a tensile tester (Model: LRX 2.5KN, LLYOD). The gauge
length of membrane sample was fixed at 50 mm and the gauge
running speed was set at 10 mm/min. The mechanical properties of the membrane were then evaluated with respect to tensile
strength and elongation using NEXTGEN software.
Membrane Porosity
The membrane porosity, , is defined as the volume of the
pores per the total volume of the porous membrane as follows:
(Wwet Wdry )
w
100
=
Wdry
(Wwet Wdry )
+
w
p

(5)

where is the membrane porosity (%), wwet is the weight of the

wet membrane (g), wdry is the weight of the dry membrane (g),
p is the density of the polymer (g/cm3 ), and w is the density
of water (g/cm3 ).
RESULTS AND DISCUSSION
Effect of Molecular Weight of PVP on Membrane
Structural Properties
Figures 3 and 4 show the SEM cross-sectional images and
3D AFM surface images of the hollow fiber membranes prepared with different Mw of PVP, respectively. It was clearly
observed that the membrane with the addition of PVP has
larger macrovoids in the sublayer in comparison to the neat
PVDF-TiO2 membrane. However, with the increase of the
PVP Mw in the dope solution, the size of macrovoids was
decreased while the sponge layer became larger. The fingerlike macrovoids gradually developed at the external and internal
surface layer with increasing Mw of PVP. The morphological
change with the PVP Mw observed by SEM can be explained by
the change in the ratio (nonsolvent inflow to the spun polymer
solution/solvent outflow out from the spun polymer solution)
during the phase inversion process and the change in the viscosity of the polymer solution. When PVP is added to the spinning
dope, the nonsolvent (water) flow into the spun polymer solution is enhanced by the presence of highly hydrophilic PVP
in the solution, resulting in the formation of large macrovoids.
This explains the increase in the size of macrovoids from PVDF

2308

C. S. ONG ET AL.

(b)

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(a)

(c)

(d)

(e)
FIG. 3. SEM cross-sectional images of PVDF-TiO2 membranes prepared from different Mw of PVP, (a) PVDF, (b) PVDF-PVP10k, (c) PVDF-PVP24k,
(d) PVDF-PVP40k and (e) PVDF-PVP360k.

to PVDF-PVP10k. However, the viscosity of the spinning dope

increases as the Mw of PVP increases (see Table 2), which suppresses the rate of nonsolvent inflow. As a result, less water
is drawn into the polymer solution, leading to a smaller size
of the macrovoids. Thus, the maximum of the macrovoid size
found at PVDF-PVP10k is the result of the interplay of the
effects of the PVP Mw on nonsolvent/solvent flow rate ratio
and the nonsolvent/solvent exchange rate. Figure 5 shows the
pore size distribution of PVDF membrane incorporated with
different Mw of PVP. The narrower pore size distribution and
smaller pore size were observed as the Mw of PVP increased
from 10 kDa to 360 kDa.
Table 3 presents several important properties of the membrane prepared from different Mw of PVP. As can be seen, an

abrupt change is noticed from PVDF to PVDF-PVP10k, which

is followed by a gradual change in the reverse direction as the
Mw of PVP increases from 10k to 360k. For example, the porosity increased from PVDF (81.95%) to PVDF-PVP10k (88.59%)
and then gradually decreased to PVDF-PVP360k (82.27%).
This change reflects the macrovoid size that also increased
from PVDF to PVDF-PVP10k and then decreased gradually
to PVDF-PVP360k. As for the properties of the membrane
surface, both the pore size and the roughness parameter (see
Fig. 4) increased from PVDF to PVDF-PVP10k, followed by
the decrease from PVDF-PVP10k to PVDF-PVP360k. This
shows a parallel relationship between the surface pore size and
the bulk macrovoid size. As more nonsolvent water is drawn
into the spun polymer solution, the larger pores and the larger

EFFECT OF PVP MOLECULAR WEIGHTS FOR OILY WASTEWATER TREATMENT PROCESS

Ra = 26.50nm

Ra = 17.58nm
(a)

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2309

(b)

Ra = 19.15nm

Ra = 16.37nm

(c)

(d)

Ra = 15.35nm

(e)
FIG. 4. 3D AFM images (outer surface) of PVDF-TiO2 membranes prepared from different Mw of PVP, (a) PVDF, (b) PVDF-PVP10k, (c) PVDF-PVP24k,
(d) PVDF-PVP40k and (e) PVDF-PVP360k.

FIG. 5. Probability density function curve generated from the pore sizes
measured by AFM for PVDF membrane prepared at different Mw of PVP.

macrovoids are formed at the membrane surface as well as

in the membrane bulk, respectively. With an increase in surface pore size, the surface roughness parameter also increases.
On the other hand, the contact angle decreases from PVDF to
PVDF-PVP10k, which is likely due to the high hydrophilicity of PVP used. Then, the contact angle keeps increasing as
the PVP Mw increases from 10 k to 360 k. This change is due
to the effect of decreasing roughness as the Wenzel equation
predicts.
To further understand the effect of membrane pore size
towards the separation efficiency, the rejection of three proteins (BSA, EA, and Trypsin) and different Mw of PVP by
the studied membranes are presented in Figs. 6 and 7, respectively. Figure 6 shows that protein rejection is in the decreasing
order of BSA > EA > trypsin except for PVDF-PVP10k membrane where the BSA rejection is lower than EA. The above
order is exactly the order of decreasing Mw (or molecular size)

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C. S. ONG ET AL.

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TABLE 3
Effect of different Mw of PVP on the PVDF-TiO2 membrane properties with respect to porosity, pore size
and contact angle
Membrane

Porosity (%)

Pore size (nm)

Contact angle ( )

PVDF (control)
PVDF-PVP10k
PVDF-PVP24k
PVDF-PVP40k
PVDF-PVP360k

81.95 1.22
88.59 3.67
85.36 6.69
85.15 3.04
82.27 8.09

121.85 1.54
134.14 1.46
119.05 1.73
114.39 1.61
106.47 1.53

75.84 2.99
59.95 1.34
66.88 0.79
69.05 0.96
85.99 3.48

FIG. 6. Rejection of BSA, EA and trypsin with different Mw of PVP on the

PVDF-TiO2 membrane (Operating conditions: temperature = 25 C, protein
concentration = 1000 ppm, pressure = 1 bar and duration = 60 min).

In other words, the protein rejection is controlled by the pore

at the membrane surface. Figure 7 illustrates the performance
of membranes in rejecting PVP of different Mw . It is to be
expected that the rejection of different Mw of PVP shows an
increasing order, which is PVP10k < PVP24k < PVP40k <
PVP360k. This order is exactly the order of increasing molecular size of the solute following an increase in Mw. Similar to the
trend observed in the protein rejection, PVP rejection of membrane decreased from PVDF to PVDF-PVP10k membrane and
increased gradually from PVDF-PVP10k to PVDF-PVP360k.
The rejection profile against protein and PVP revealed that the
separation efficiency of the UF membrane was mainly governed
by the surface pore of the membrane itself.
Table 4 illustrates the mechanical properties of PVDF-TiO2
membrane with different Mw of PVP. Upon addition of PVP
regardless of their Mw , all PVP containing membranes demonstrated decrease in the tensile strength and elongation-at-break.
The deterioration in mechanical strength can be reasonably
explained by the formation of macrovoids in the membrane sublayers as evidenced in the SEM cross-section images. Although
the mechanisms involved have not been clearly established, but
it has been proposed that the formation of macrovoid would act
as weak points of the whole membrane integrity and result in
high tendency of membrane structure collapse as compared to
neat PVDF membrane (14, 30). However, it is worth mentioning that the deterioration in the membrane mechanical strength
has negligible effect on our present study as the submerged UF
membrane system only applied very low vacuum pressure.
TABLE 4
Effect of different Mw of PVP on the PVDF-TiO2
membrane properties with respect to mechanical strength

FIG. 7. Rejection of different Mw of PVP on the PVDF-TiO2 membrane prepared with different Mw of PVP (Operating conditions: temperature = 25 C,
PVP solution concentration = 1000 ppm, pressure = 1 bar and duration =
60 min).

of the proteins. Furthermore, the protein rejection decreased

from PVDF to PVDF-PVP10k membrane and increased gradually from PVDF-PVP10k to PVDF-PVP360k. This trend is
exactly the same as the trend observed by the surface pore size.

Membrane
PVDF (control)
PVDF-PVP10k
PVDF-PVP24k
PVDF-PVP40k
PVDF-PVP360k

Tensile strength
(MPa)

Elongation-at-break
(%)

2.77 0.16
2.05 0.16
2.14 0.34
2.18 0.19
2.57 0.10

351.50 110.69
300.34 111.59
310.36 135.12
312.00 103.08
344.50 136.49

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EFFECT OF PVP MOLECULAR WEIGHTS FOR OILY WASTEWATER TREATMENT PROCESS

Effect of Different Molecular Weight of PVP on

Membrane Flux and Oil Rejection
Figure 8 shows the results from the experiments conducted using pure water and synthesized oily wastewater. From
Fig. 8(a), the pure water flux (Jw1 ) was reported to increase
from PVDF to PVDF-PVP10k and gradually decreased from
PVDF-PVP10k to PVDF-PVP360k. This pattern is exactly the
same as those observed in the surface pore size and the bulk
porosity. It seems natural that Jw1 increases as both surface pore
size and bulk porosity increase. The pattern observed in Jw1 is
also exactly the same as the pattern observed in hydrophilicity,
i.e., the hydrophilicity increased, shown as the decrease in contact angle (see Table 3) from PVDF (control) to PVDF-PVP10k
membrane and decreased gradually from PVDF-PVP10k to
PVDF-PVP360k. Hence the increase in surface hydrophilicity
is also contributing to greater Jw1 .

2311

The permeate flux of the oil/water mixture (Jw2 ) was slightly

lower than Jw1 . Interestingly, the flux ratio of Jw2 /Jw1 illustrated in Fig. 8(b) shows the pattern of PVDF < PVDF-PVP10k
> PVDF-PVP24k > PVDF-PVP40k > PVDF-PVP360k. The
decrease of the Jw2 /Jw1 ratio with increasing Mw of PVP can
be attributed to the rapid formation of oil layer on the membrane surface, which has led to the increase in water transport
resistance (30). On the other hand, a reverse pattern of PVDF >
PVDF-PVP10k < PVDF-PVP24k < PVDF-PVP40k < PVDFPVP360k, was observed in oil rejection. It could be explained
by the increase of membrane hydrophobicity with the increasing of PVP Mw (as shown in Table 3) which has facilitated
stronger interaction between the membrane surface and the oil
layer. Thus, more oil particles are adsorbed and attached on
the membrane surface, resulting in thicker oil layer formation
and higher oil rejection. Overall, it can be said that PVDFPVP40k is the best performing among the studied membranes
due to its good combination of water permeability and oil
selectivity.
Effect of pH on Membrane Performance
To further understand the performance of the PVDFPVP40k membrane, the effect of feed pH on the membrane
water flux and rejection during oily wastewater treatment
was evaluated by varying the feed pH in the range of 410.
As shown in Fig. 9, the membrane achieved the lowest flux
at pH 4 (41.58 L/m2 .h) followed by pH 10 (53.50 L/m2 .h)
and pH 7 (72.15 L/m2 .h). Interestingly, the trend observed in
permeate flux is reverse of the pattern found in membrane separation efficiency, i.e., the lowest the permeate flux the highest
the oil rejection, and vice versa. In comparison to the neutral
condition, the decrease in membrane permeate flux at acidic
and alkali environment is most likely due to the rapid fouling

FIG. 8. (a) Pure water flux (Jw1 ) and permeate flux (Jw2 ) (b) oil rejection
(%) and ratio of Jw2 / Jw1 of PVDF-TiO2 membranes prepared at different
Mw of PVP (Operating conditions: temperature = 25 C, oil concentration =
250 ppm, air bubble flow rate = 5 L/min and vacuum pressure = 15 inHg,
Mw = 0 means PVDF-TiO2 membrane without PVP).

FIG. 9. Effect of feed pH on the permeate flux and oil rejection of PVDFPVP40k membrane (Operating conditions: temperature = 25 C, oil concentration = 250 ppm, air bubble flow rate = 5 L/min and vacuum pressure =
15 inHg).

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2312

C. S. ONG ET AL.

resulted from greater oil rejection efficiency. This phenomenon

is mainly due to the existence of charges on membrane surface
at pH 4 and 10. Furthermore, the surface charge of membrane
at pH 7 is at the lowest level since the isoelectric point (IEP) of
P25 TiO2 (which embedded in membrane matrix) is at between
pH 6.2 and 6.9 as reported elsewhere (31, 32). Therefore, the
membrane would carry no net surface charge at pH near to
7 which allows more oil particles passing through the membrane and further results in lower rejection as experienced in
this work. Similar findings were also reported by Hua et al.
(33) in which they found that membrane achieved the lowest
flux at pH 3.8 in comparison to other pHs ranging from 4 to
10. However, it must be pointed out that they attributed the low
permeability of membrane to the better stability of oil droplets
at acidic environment instead of to severe fouling problem as
elucidated by us.
Effect of Oil Concentration on Membrane Flux and Oil
Rejection
To further investigate the separation performance of PVDFPVP40k membrane, the oil concentration of the oily solution
was varied between 250 ppm and 1000 ppm. The normalized
water flux and oil rejection of the membrane as a function of
time are shown in Fig. 10. It is found that at low oil concentration the decline of membrane flux is not as severe as that
observed at high oil concentration. For 250 ppm oil solution,
the membrane flux declined around 19% in 180 min compared
to 30% and 33% recorded for 500 ppm and 1000 ppm oily
solution, respectively. The increase in flux decline rate can be
explained by a thicker oil layer formed on the membrane surface at high concentration of the oily solution which causes
water transport resistance to increase and water flux to decrease
(30). Additionally, the hydrophobicity of the membrane has
also increased as indicated by the increase in contact angle. This
has further enhanced the interaction between the membrane
surface and the oil layer, causing more oil particles attached
and absorbed on the membrane surface and contributing to
membrane flux deterioration.
Despite the flux decline, the increase in oil rejection with the
increasing oil concentration is observed in Fig. 10(b). This phenomenon is expected as oil droplets are likely to be adsorbed
and attached on the membrane surface, resulting in thicker oil
layer formation as the oil concentration increases, which leads
to higher oil rejection. At 250 ppm, the initial oil rejection was
around 70%, but was slowly increased with time and eventually achieved 97% removal of oil. Similar increasing trend
was also observed in the oil concentration of 500 ppm and
1000 ppm, although higher oil concentration could achieve
relatively higher oil rejections at the early stage of the filtration
process.
Effect of Cleaning Process on Membrane Water Flux and
Oil Rejection
In order to assess the extent of fouling on the membrane performance with respect to water flux and rejection,

FIG. 10. Filtration experiments of PVDF-PVP40k membrane at different oil

concentrations (a) Normalized flux ratio and (b) Oil rejection (Operating conditions: temperature = 25 C, air bubble flow rate = 5 L/min and vacuum
pressure = 15 inHg).

PVDF-PVP40K membrane was subject to backflushing cleaning process using deionized water for 60 min after being used
for treating oily solution of 250 ppm for up to 3 h. Figure 11
compares the performances of the membrane as a function of
time before and after cleaning process. The results revealed that
the approximately 60% of the initial flux of membrane could
be retrieved by a simple backflushing cleaning process without
involving any chemical agents and optimized cleaning conditions. Further increase in membrane flux recovery rate can be
practically conducted, provided the chemical cleaning solution
used is mild to the membrane structural properties. Even though
the membrane water flux was not able to be completely recovered by backflushing process, it is interesting to note that no
significant difference was experienced in separation efficiency
as the membrane tended to achieve a promising rejection rate

EFFECT OF PVP MOLECULAR WEIGHTS FOR OILY WASTEWATER TREATMENT PROCESS

2313

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reversible fouling as the flux could be significantly retrieved by

simple water backflushing process. With respect to oil rejection,
it is found that the excellent separation efficiency of membrane
after cleaning process is slightly affected (less than 2% reduction). Based on the results obtained in this work, it is showed
that PVP is a very good additive in improving the properties
of PVDF-TiO2 composite membrane by enhancing not only
membrane permeability but also selectivity, making the modified composite membrane a good candidate for sustainable
development of oily wastewater treatment.
ACKNOWLEDGEMENTS
The authors would like to thank the management support from the Research Management Centre (RMC), Universiti
Teknologi Malaysia.
FUNDING
The authors gratefully acknowledge the financial support
from the European Commission FP7 - LIMPID (Project number: 310177).
SUPPLEMENTAL MATERIAL
Supplemental data for this article can be accessed on the
publishers website.
REFERENCES
FIG. 11. Comparison the performances of PVDF-PVP40k membrane as a
function of time before and after cleaning process, (a) permeate flux and flux
recovery and (b) oil rejection (Operating conditions: temperature = 25 C,
oil concentration = 250 ppm, air bubble flow rate = 5 L/min and vacuum
pressure = 15 inHg).

against oil particles (> 95%) after 150 min of the filtration
process.
CONCLUSIONS
The permeation performance of PVDF-TiO2 membranes
with different Mw of PVP was evaluated for the treatment of
aqueous protein solution and oil/water mixture. The results
obtained showed that the membrane properties were affected
with the use of different Mw of PVP as additive during membrane preparation. Based on the results obtained from this study,
the addition of PVP to PVDF membrane could improve the
hydrophilicity, pore size, and porosity of the PVDF membrane.
Among the PVDF-PVP membranes studied, it can be concluded that PVDF-PVP40k is the best performing membrane
due to its high permeability and selectivity achieved during oil
filtration experiment. Experimental results also revealed that the
membrane flux reduction during filtration is mainly due to the

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