Colloids and Surfaces A: Physicochem. Eng.

Aspects 516 (2017) 147–160

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Surface modification of polyacrylonitrile ultrafiltration membranes

using amphiphilic Pluronic F127/CaCO3 nanoparticles for oil/water
emulsion separation
J.S. Beril Melbiah, D. Nithya, D. Mohan ∗
Membrane Laboratory, Department of Chemical Engineering, Anna University, Chennai 600025, India

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

• Highly hydrophilic
PAN/PF127/CaCO3 membranes
were fabricated for the separation
oil-water emulsion.
• Membrane properties were
enhanced upon addition of max-
imum dosage of CaCO3 nanoparticle
with PF127.
• As high as 90% of water flux could
be recovered for the modified mem-
brane on cleaning with water.
• Enhanced hydrophilicity coupled
with large number of pores on mem-
brane surface was the key factor for
the excellent antifouling property of
the modified membrane.

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

Article history: In this work, flat sheet polyacrylonitrile (PAN) based ultrafiltration (UF) membranes were fabricated by
Received 29 August 2016 blending with amphiphilic copolymer Pluronic F127 (PF127) and inorganic calcium carbonate (CaCO3 )
Received in revised form nanoparticles by nonsolvent induced phase inversion process which was employed as fouling resis-
23 November 2016
tant membranes for the separation of oil-water emulsion mixture. CaCO3 nanoparticle was synthesized
Accepted 8 December 2016
by controlled precipitation of saturated carbonate and calcium nitrate aqueous solution and was then
Available online 9 December 2016
confirmed by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction spectroscopy (XRD) and
high-resolution transmission electron microscopy (HR-TEM). The fabricated membranes were charac-
Keywords:
Hydrophilicity
terized by attenuated total reflectance infrared spectroscopy (ATR-FTIR), thermal gravimetric analysis
PAN membrane (TGA), mechanical analysis, scanning electron microscopy (SEM), atomic force microscopy (AFM) anal-
CaCO3 nanoparticle ysis to study the effect on the addition of PF127 together with varying amount of CaCO3 nanoparticle
Pluronic F127 dosage on the membrane property. The filtration performances of the membranes were evaluated by mea-
Oil-water emulsion suring pure water flux, molecular weight cut off (MWCO), porosity and water content. The membrane
hydrophilicity/hydrophobicity was examined through water contact angle measurement and separa-
tion efficacy was measured through ultrafiltration of oily feed solution. Membrane properties such as
wettability, pure water permeability, mechanical strength, thermal stability, oil removal efficiency of
the modified membrane was found to increase high upon addition of 0.75 wt% of CaCO3 nanoparticle.

∗ Corresponding author.
E-mail addresses: berilmelbiah@gmail.com (J.S.B. Melbiah), nithyarabekkal@gmail.com (D. Nithya), mohantarun@gmail.com (D. Mohan).

http://dx.doi.org/10.1016/j.colsurfa.2016.12.008
0927-7757/© 2016 Elsevier B.V. All rights reserved.
148 J.S.B. Melbiah et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 516 (2017) 147–160

Flux recovery was found to elevate from around 63% to 90% after a simple hydraulic wash indicating that
the modified hybrid membranes were less susceptible to fouling. The increase in water permeability and
antifouling property is ascribed the presence of large number of hydroxyl functional groups coupled with
large number of small pores on the modified membrane surface.
© 2016 Elsevier B.V. All rights reserved.

and magnetic materials have also been implemented [10,11]. Low

Nomenclature separation efficiency, large amount of secondary sludge produc-
tion, high capital cost are the factors that limit the efficiency of the
L Mean size of the crystallite (nm) aforementioned processes. More importantly, 99% of oil removal
K Crystallite shape factor cannot be achieved efficiently with those methods.
␭ X-ray wavelength In the last few decades, membrane filtration, which primarily
ˇ FWHM (full width at half max) functions by size exclusion, is proven to be a promising candi-
 Bragg angle (deg) date for the effective separation of emulsion containing micron and
Cf Concentration of the feed (ppm) submicron sized oil droplets. Its unique features including being
Cp Concentration of the permeate (ppm) eco-friendly, high separation efficiency, low energy consumption,
M Molecular weight cut off of the corresponding mem- low foot print, less chemical addition make it advantageous to
brane achieve high removal of oil molecules from oil water mixture over
␸w Membrane porosity (%) the other conventional processes [12]. Amongst the pressure driven
W0 Wet weight of membrane (g) membrane processes (MF, UF, NF, RO) which have been widely
W1 Dry weight of membrane (g) employed for the separation of aqueous mixtures, Ultrafiltration
␳w Density of water (g/cm3 ) (UF) which has a pore size ranging from 2 to 50 nm is found to be
L Membrane thickness (cm) an efficient method for the separation of oil droplets having micro
Q Volume of water permeated (L) meter range in a single unit without demulsification [13]. However,
t Water permeation time (h) membrane oil fouling is a major limiting factor in this case owing to
A Effective area of membrane (cm2 ) the intrinsic hydrophobic nature of the polymeric membrane used
Jw Pure water flux (L/m2 h) as they exhibit adhesion and deposition of oil droplets onto the
Jo Permeation flux for emulsion (L/m2 h) membrane surface. Oil is considered as a spreadable foulant which
Jwo Pure water flux after cleaning the membrane with is much more unstable when compared with other macromolecu-
water (L/m2 h) lar foulant like protein. Imparting oil foulants onto the membrane
Jw1 Permeation flux for emulsion after cleaning the surface deteriorates membrane performance in terms of flux dec-
membrane with water (L/m2 h) lination and recyclability.
Jw2 Pure water flux after cleaning the membrane with A well patterned compact water layer that is formed effec-
SDS solution (L/m2 h) tively through hydrogen bonding or electrostatic interaction can
Wa Work of adhesion (mN/m) act as a barrier for the prevention of direct adhesion of oil foulant
Sc Spreading coefficient (mN/m) onto membrane surface. This can be achieved by introducing a
␥sl Interfacial free energy (mN/m) hydrophilic moiety onto the membrane surface that enhances the
␥sv Surface free energy (mN/m) antifouling property [14]. The hydrophilic polar groups at mem-
FRR Flux recovery ratio (%) brane surface easily binds with the surrounding water molecules
DRt Total flux decline ratio (%) through hydrogen bonding. Apart from that, emulsion is a liquid-
DRr Reversible flux decline ratio (%) liquid colloidal system containing dispersion of finely divided oil
DRir Irreversible flux decline ratio (%) droplets in abundant water. In this regard, the removal of water is
fairly easier. Hydrophilic surface usually favors diffusion of water
molecules through membranes while repelling the hydrophobic
1. Introduction oil molecules [15]. The sieving effect of membranes as well as the
membrane fouling is all related to the hydrophilic extent at the
In recent years, the dramatic increase in release of oily wastew- membranes surface. The method of implanting hydrophilic group
ater from various industries such as textile, leather processing, over polymer surface such as surface coating, uv-irradiation, graft-
petrochemical, food processing as well as frequent oil spill acci- ing have been widely investigated. These methods are complex
dents pose a huge threat to the ecosystem [1,2]. This paves way in their action and need more harsh chemicals as additive. For
for environmental pollution which is an alarming situation at this instance, delamination is possible in the case of surface coating.
juncture. The oily wastewater comprises of sticky oily substances, A more advantageous simple technique of blending with dis-
harmful chemicals and miscible organics at a concentration level tinct materials and properties can yield a membrane with tunable
ranging from 100 to 1000 mg/L which is not permissible to human properties such as high water flux, porosity, antifouling property,
health, ultimately endowing a negative impact on environment. mechanical durability and thermal stability. Polyacrylonitrile (PAN)
Efforts have been taken extensively to minimize the concentration is a versatile polymer that has been widely employed for preparing
level to 10 mg/L to meet the environmental regulatory standard [3]. membranes owing to its good tolerance to solvents and chlorine
Moreover, separation of surfactant stabilized oil-water emulsion [16,17]
of micron and submicron (below10 ␮) is ineffective with tradi- Incorporation of macro molecular additives such as PVP, PEG,
tional methodologies such as centrifugation, gravity separation, PF127 is known to pose excellent antifouling property in mem-
mechanical coalescence, depth filtration, settling tanks, dissolved branes. Heru Susanto et al., investigated the effect of different
air floatation, ultrasonic irradiation, and rotating disk filtration macromolecules such as PVP, PEG, PF127 on PES membrane [18].
[4–9]. Recently, new techniques such as incorporation of aerologels
 J.S.B. Melbiah et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 516 (2017) 147–160
The addition of PF127 had the best overall performance in terms
of flux increment and showed excellent antifouling ability. Intro-
duction of PF127 generates a unique self assembling behavior
through which the hydrophilicity is enhanced in polymeric mem-
branes such as CA, PES, PVC, PVDF, PEI, PSF which eventually leads
to the improved performance in separating aqueous mixture and
antifouling property respectively [19–24]. PF127 is an amphiphilic
co-polymer with a structure of PEO-PPO-PEO which is a non-ionic
macromolecule commercially available as Poloxamer or Pluronics,
serves a dual role as pore former and membrane modifier [25]. Dur-
ing demixing and subsequent coagulation, only a part of PF127
segment will be entangled in between the polymeric chains. In
that, the hydrophilic segment PEO instantaneously tend to seg-
regate at membrane-water interface while the counterpart, PPO
moiety gets anchored onto the membrane matrix. Further, a major
portion of PF127 self assembles into spherical micelles with the
shell configuration. These micelles tend to leach out in the coagu-
lation bath forming macrovoids in the membrane. The appearance
of macrovoids is not desirable as it diminishes the mechanical
strength of membrane. Similar effects have been noticed on adding
PF127 with polymeric membranes such as PVC and PVDF [21,22].
Mechanical stability is an important parameter for the durability
and long term performance of the membrane. Addition of inor-
ganic nanoparticles into the casting solution not only increases the
mechanical stability but also improves the overall performance of
the membrane owing to its high aspect ratio, macroscopic quantum
effects etc. Incorporation of hydrophilic nanoparticles into poly-
meric membrane matrix such as Bentonite [26], Magnesium Oxide
[27], Hydrous Aluminium Oxide [28], Silicon di oxide [29], Hydrous
Manganese Oxide [30] etc., have shown excellent performance in
the filtration of oil-water emulsion.
Here we have used a cheap nanomaterial CaCO3 , which is com-
mercially available in abundance and can easily be synthesized.
They find enormous applications in the manufacture of plastics,
rubber, paints. Studies reveal that CaCO3 was frequently employed
to improve mechanical durability of polymer composites [31,32].
More importantly, addition of CaCO3 in Polysulfone membrane has
improved its antifouling as well permeation property [33]. Wu et
al., showed that membranes impregnated with nano CaCO3 exhib-
ited increased porosity which was advantageous for rapid water
permeation [54]. Ca2+ ion of CaCO3 interacts effectively with water
through hydrogen bonding of electrostatic attraction which can
enhance hydrophilicity. Further, for the efficient filtration of oil-
water mixture, the pore size of the membrane should be smaller
than the least size of oil droplets or else it may lead to squeezing
of oil droplets through such pores. Then it is imperative to make a
membrane of desirable pore size for the effective separation.
Our aim is to develop a membrane with hierarchal structur-
ing by tuning hydrophilicity as well as pore geometry that enables
complete separation of oil-water emulsion mixture to achieve high
selectivity and permeation at the same time maintaining mechan-
ical durability.
In this paper, we have attempted to develop a highly hydrophilic
membrane containing nanoporous skin layer integrated to a micro-
porous support via. phase inversion so that the membrane could
be employed for efficient separation of emulsion droplet below
10 ␮m. To the best of our knowledge, there is no study focus-
ing on PAN/PF127/nano CaCO3 hybrid membranes. In this work,
PAN based membranes modified with PF127 and nano CaCO3 were
prepared through phase inversion technique. Structural and mor-
phological analysis of the modified membrane was carried out
by means of SEM, AFM. The successful incorporation of CaCO3
nanoparticle and PF127 on membrane matrix was confirmed by
ATR-FTIR analysis and hydrophilicity was evaluated by goniome-
ter. Separation performances of all the prepared membranes were
149
examined with respect to pure water flux, oil rejection, water flux
recovery and fouling resistance.
2. Experimental
2.1. Materials
PAN based UF flat sheet membranes were prepared using
Polyacrylonitrile (PAN, MW: 150,000 g/mol) obtained as a gift sam-
ple from Technorbital, Uttar Pradesh, India. Pluronic F127 (M.W:
12,600 g/mol) and Tween 80 were purchased from Sigma Aldrich.
The solvent N-methyl-2-pyrrolidone (NMP) from SRL Chemicals
Ltd., India was sieved through molecular sieves (4 A0 ) in order to
remove moisture and stored in dry conditions prior to use. Sodium
carbonate (Na2 CO3 ), sodium hydroxide (NaOH) and calcium nitrate
tetrahydrate (Ca(NO3 )2 ·4H2O) were purchased from Merck, India
Ltd. Sodium lauryl sulfate (Glaxo India Ltd.) and was used as surfac-
tant. A series of PEGs from Merck were used to evaluate the MWCO
of the membranes.
2.2. Synthesis of CaCO3 nanoparticles
The synthesis of CaCO3 nanoparticle was done by precipitation
technique based on the literature survey [34]. The solution ‘A’ was
prepared by dissolving 0.1 M of Na2 C03 in deionised water along
with 0.2 M of NaOH and 0.18 M of CaCl2 . A solution ‘B’ contain-
ing 0.1 M of Ca(NO3 )2 was also prepared. Subsequently, solution ‘B’
was added in dropwise to the solution ‘A’ under vigorous stirring
at determined agitation speed. The turbid solution mixture thus
obtained was kept at constant mechanical stirring for about one
hour. The end product was centrifuged and dried to obtain CaCO3
nanoparticles.
2.3. Characterization of CaCO3 nanoparticles
2.3.1. Fourier transform infrared spectroscopy (FTIR)
The IR spectrum for the synthesized CaCO3 nanoparticle was
recorded by the KBr pellet method with a spectrometer (Spectrum
RXI, Perkin Elmer) in the range of 4000–400 cm−1 .
2.3.2. X-ray diffraction (XRD) analysis
The XRD pattern for the synthesized nanoparticles was recorded
using Wide Angle Diffraction pattern on a Bruker AXS D8 Advance
X-ray diffractometer. The X-Ray diffractograms were obtained
using Cu K␣ (␭ = 1.5406 A◦ ) between 20◦ to 80◦ at a radiation speed
of 2◦ per minute. The crystalline size of CaCO3 is calculated from
Debye-Scherrer Equation [35]. The Scherrer formula is expressed
as follows.
K
L= (1)
ˇcos
Where, L, mean size of the crystallite (nm); K, crystallite shape fac-
tor; ␭, X-ray wavelength; ˇ, FWHM (full width at half max); , Bragg
Angle (deg).
2.3.3. Transmission electron microscope (TEM)
The morphology as well as the size of synthesized CaCO3
nanoparticle can be analyzed using Transmission Electron Micro-
scope with JEM-3010 TEM (Joel Ltd, Tokyo, Japan) operated at a
voltage of 200KV. The powdered sample was suspended in abso-
lute alcohol and sonicated for 5 min to make it as a fine dispersion.
A drop of the resulted suspension was placed on the carbon coated
copper grids and allowed to dry at ambient temperature. Final dried
particles were then observed through TEM.
150 J.S.B. Melbiah et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 516 (2017) 147–160
Table 1
Composition of the prepared membranes.
Membrane PAN (wt%) PF127 (wt%)
MA 9 0
M0 9 1
M1 9 1
M2 9 1
M3 9 1
2.4. Fabrication of membranes
Flat sheet PAN, PAN/PF127, PAN/PF127/CaCO3 nanoparticle
hybrid membranes were fabricated via. phase inversion technique
(Immersion Precipitation). Prior to blending of polymer with sol-
vent, predetermined amounts of CaCO3 nanoparticle was added
to the solvent, NMP and was sonicated for certain time to avoid
aggregation and to ensure fine dispersion. Aggregated nanoparti-
cles would block the pores by clogging into the pore channels. After
sonicating, 9 wt % of polymer PAN followed by 1 wt % of PF127 was
added to the fine suspension and it was kept for mechanical stir-
ring for six hours until the polymer dissolved out completely to
form homogeneous solution. The blended solutions were kept for
deaeration for the complete removal of air bubbles. Dope solution
thus produced was then casted onto a fine grade polished substrate
using a casting knife with a specific gap height. Subsequently, the
glass plate was immersed into a coagulation bath where demix-
ing and then preciptaion to occur. Then it was kept overnight
as such for the completion of solvent-non solvent exchange pro-
cess. The membranes were then peeled off from the glass plate,
washed in distilled water thoroughly to remove excess traces of
NMP. PAN/PF127 membrane was prepared in the same way without
nanoparticle addition and the pristine PAN membrane was pre-
pared in the same manner without additives [36]. The composition
of the casting solution for each membrane is given in Table 1
2.5. Analysis of membranes
2.5.1. Analysis of molecular weight cut off (MWCO), pore size,
porosity and equilibrium water content (EWC)
MWCO of each membrane was measured by using a series of
PEG solution (2 wt%). The concentration of feed, rejection and per-
meation was determined using TOC (Shimadzar, TOT-VCPH). The
percentage rejection of solute (SR) was calculated by using the
formula
 Cp
 gen atmosphere. The samples were heated upto a temperature of
SR (%) = 1− × 100
Cf
where, Cf is the concentration of the feed and Cp is the concentration
of the permeate.
The MWCO and pore size of membrane is inter related. The
mean pore size was calculated from the obtained MWCO values.
The membrane that showed more than 80% of solute rejection was
taken as the MWCO, of the corresponding membrane. The pore
radius of each membrane was found out by using the following
formula.
   ducing electron conductivity. Cross sectional images were captured
g under vacuum at 15KV.
r = (0.0262nm) M − 0.03nm
mol
Membrane porosity (␸w ) is to measure water upholding capac-
ity of membranes. Porosity was calculated by the following
expression.
W0 − W1
ϕw = × 100
wAL
CaCO3 (wt%) Solvent, NMP
(wt%)
0 91.0
0 90.0
0.25 89.75
0.5 89.5
0.75 89.25
where, W0, wet weight of membrane; W1, dry weight of mem-
brane; ␳w, density of water; A, membrane active area; L, membrane
thickness.
Equilibrium water content (EWC) is related to porosity and
hydrophilicity. As prepared membranes were soaked in water for
24 h and weighed them after mopping with blotting paper. These
wet membranes were dried in a vacuum for 48 h and the dry
weights were determined. From these two values, the water con-
tent was calculated by using the following equation.
W0 − W1
EWC = × 100 (5)
W0
The results of MWCO, porosity, water content and mean pore
size are presented in Table 2.
2.5.2. Attenuated total reflection–Fourier transform infrared
(ATR-FTIR) analysis
ATR-FTIR was carried out to reveal the functional groups present
in the composite membrane surface. FTIR Spectra of the mem-
branes were determined using Attenuated Total Reflectance (ATR)
technique with a spectrometer (Spectrum RXI, Perkin Elmer) in the
range of 4000–400 cm−1 .
2.5.3. Mechanical property (UTM)
The tensile strength of the prepared membranes was deter-
mined using ASTM D8882 standard with an Instron 3369 analyzer.
The extension rate was 10 mm/min. All samples were cut to 12
cmx3 cm in ambient condition (25 ◦ C, relative humidity of 68%).
Excess water was mopped before testing. The tensile strength was
determined from stress-strain curve. The average value of three
trails was reported for each membrane.
2.5.4. Thermal gravimetric analysis (TGA)
The thermal behavior of pristine and composite membranes
was examined using universal V4.5A TA DTG analysis in a Nitro-
(2) 800 ◦ C at a heating rate of 20 ◦ C/min.
2.6. Morphological analysis of membrane
2.6.1. Scanning electron microscopy (SEM)
The cross sectional images of all the membrane samples were
observed by Scanning Electron Microscope (SEM, Cam Scan). Sam-
ples were cut in 1 cm × 1 cm. The excess water on membrane was
mobbed with blotting paper and fractured in liquid Nitrogen (N2 )
for 60 s. All the frozen membranes were sputtered with gold for pro-
(3)
2.6.2. Atomic force microscopy (AFM)
Atomic Force Microscopy (Park System, Korea model no. XE-
100) was used to know the topography and roughness of the
membrane surface. Small squares of the prepared membranes of
size 1 cm × 1 cm were glued on a glass substrate and surfaces were
(4)
imaged in a scan size of 2 ␮m × 2 ␮m by using the tapping mode.
 J.S.B. Melbiah et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 516 (2017) 147–160 151

Table 2
Molecular Weight Cutoff (MWCO), Porosity, Water content and Mean pore radius for pure and modified PAN membranes.

Membrane Porosity (%) Water content (%) MWCO (kDa) Mean pore size (A◦ )

MA 74.3 67.8 25 41.13

M0 81.5 73.0 70 69.0
M1 80.0 70.5 40 52.1
M2 2.7 73.9 35 48.7
M3 85.8 77.2 35 48.7

in turn was connected to a compressor with a pressure control valve

Fig. 1. Size distribution of oil droplets in the synthesized oil/water emulsion.
2.7. Membrane wetting property
The wettability of all the prepared membranes was examined by
measuring its water contact angle (WCA) using sessile drop tech-
nique. Initially the excess moisture was mopped with a blotting
paper on the membrane surface. Followingly, a volume of 5 ml of
Milli-Q water was placed on the membrane surface using a syringe
and the contact angle was captured within first 10 s at ambient
temperature by contact OCA 15EC, Data Physics, Germany. For each
membrane, contact angle was measured at five different locations
and the average was then taken for accuracy. From the contact
angle measured, the interfacial free energy (␥sl ), surface free energy
(␥sv ), work of adhesion (Wa) and Spreading coefficient (Sc) was
calculated using following equations.
sl = sv − lv cos
 
Wa = 1 + cos lv
Sc = sv − sl − lv
2.8. Oil/water emulsion separation experiment
2.8.1. Preparation of synthetic oily wastewater
Surfactant stabilized oil-in-water emulsion was prepared by
adding Tween 80 as emulsifier. 1 g of Tween 80 was added in to
1L of water, then 1 ml of oil (Motor Oil) was added to it. The mix-
ture was stirred using a mechanical blender for about one hour to
obtain a stable emulsion. The average size of the oil droplets in the
prepared emulsion was measured by Malvern Zetasizer, Nano ZS
instrument and it was found to be in an average size of 5 ␮m as
shown in Fig. 1.
2.8.2. Ultrafiltration test
The performance of all the prepared membranes were examined
in terms of its permeation and rejection property using batch type
dead end UF cell fitted with a Teflon-coated magnetic paddle which
and gauge through a feed reservoir. The inner diameter of UF cell
(Model 800, Amicon) was 7.6 cm and effective area was 45.38 cm2
with a volumetric capacity of 350 ml. The UF setup used for this
experimental study is similar to the setup reported by Jaya et al.
[37]
Freshly prepared membranes without any further treatment
were mounted on the filtration cell. Firstly, the membranes were
precompacted at a constant pressure of 60 psi for an hour using dis-
tilled water taken in the solution reservoir. Subsequently, pressure
was released down to 30 psi and permeate was measured at regular
intervals until a steady state was obtained. The pure water flux (Jw )
was calculated based on the following expression.
Q
Jw = (9)
A.t
Q is the volume of water permeated (L); t is the water permeation
time (h); A is the effective area of membrane (m2 )
Followingly, the solution reservoir was filled with oil-water
emulsion mixture. The permeation flux for emulsion was calcu-
lated as (Jo ) which was calculated from the measured quantity of
permeated water recorded at regular intervals. The solute rejec-
tion (SR) on emulsion filtration was calculated from finding the
concentration values of feed solution and permeate flux using total
organic carbon analyzer (Shimadzu, TOC-VCPH) using the following
equation.
Cp
SR(%) = (1 − ) × 100 (10)
Cf
In order to assess the antifouling property of all the membranes,
the membranes were removed and subjected to hydraulic washing
for 20 min and mounted back again. The flux (Jwo ) was calculated
based on the measured quantity of permeate recorded at regular
intervals. The efficiency of membranes in terms of oil fouling resis-
tant property was evaluated from Flux Recovery Ratio (FRR) and
(6) Decline Ratio (DR), by using the following equation.
J 
(7) Flux Recovery Ratio, FRR =
wo
× 100 (11)
Jw
(8)  Jwo − Jo 
Reversioble Flux Decline = DRr × 100 (12)
Jw
 Jw − Jwo 
Irreversible Flux Decline, DRirr = × 100 (13)
Jw
 Jw − Jo 
Total Flux Decline, DRT = × 100 (14)
Jw
Total Flux Decline is the summation of Reversible and Irre-
versible Flux Decline. It is known that higher FRR values and lower
DR values is the indication of better antifouling property of mem-
brane. Again the flux for oil water emulsion was recorded as (Jw1 )
which was measured by refilling the solution reservoir with emul-
sion mixture. Further, the reliability of the membranes for its
practical application and for its long term run was tested by wash-
ing the fouled membranes with SDS solution and measuring pure
water flux as (Jw2 ) in the same aforementioned manner. The DR and
FRR values were also calculated in the same way.
152 J.S.B. Melbiah et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 516 (2017) 147–160

Fig. 2. FTIR analysis of synthesized CaCO3 nanoparticle.

4. Results and discussion Fig. 3. Transmission electron microscope (TEM) micrograph of calcium carbonate
(CaCO3 ) nanoparticles.

4.1. FTIR of CaCO3 nanoparticle

FTIR spectrum was analyzed to identify the surface chemi-

cal composition. The FTIR obtained for the synthesized CaCO3
nanoparticle is shown in Fig. 2. The peaks obtained at 3380 cm−1
and 3178 cm−1 are ascertained to the stretching vibration of OH
group owing to the presence of moisture content on the surface
of calcium carbonate nanoparticle [38]. The weak peak seen at
2686 cm−1 is attributed to C O symmetric stretching. Another
peak at 1408 cm−1 is ascribed to the stretching frequency C O
(Carbonate asymmetric stretching) [39]. The sharp peak found at
1081 cm−1 , 1408 cm−1 , 725 cm−1 corresponds to the in-out plane
bending and asymmetrical stretching vibrational peaks of O C O.
The peaks obtained confirm the successful formation of calcium
carbonate nanoparticle [40].

4.2. Morphology and structure of CaCO3 nanoparticle

Fig. 3 displays the TEM micrograph obtained for CaCO3 nanopar-

ticles. TEM micrographs indicate no aggregation of nanoparticles
Fig. 4. X-ray diffraction spectroscopy (XRD) of calcium carbonate (CaCO3 ) nanopar-
wherein the nanoparticles appears to be uniformly cubic in shape ticles.
[41]. The average particle size is ranging in between 71 nm and
96 nm. XRD pattern obtained for the synthesized CaCO3 is depicted
in Fig. 4. The reflection pattern of nanoparticle reveals that CaCO3
nanoparticles are in calcite form. The profile obtained did not have
any peaks of Aragonite or Vaterite which is in good agreement with
literature data [33,42]. These characteristic peaks obtained confirm
the crystallographic form of calcite. The absence of uncertain peaks
indicates that high purity of CaCO3 nano powder [43].
From Sherrer equation [35], the average crystalline size is found
to be 81 ± 2 nm which is more or less equal to the crystalline size
obtained from TEM results.

4.3. ATR-FTIR analysis

The observed ATR-FTIR spectra of pristine and hybrid mem-

branes are depicted in Fig. 5. The broad absorption band at
3367 cm−1 is assigned to the presenc of OH, NH groups. It is inferred
that intensity of this characteristic broad peak is increasing grad-
ually with increase in dosage of CaCO3 nanoparticles. The peaks
around 2280 cm−1 correspond to the CH vibration of methylene. On
comparing with pristine PAN, the intensity of this (methylene) peak Fig. 5. ATR-FTIR spectra of pure PAN and modified PAN membranes.
 J.S.B. Melbiah et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 516 (2017) 147–160
Fig. 6. Tensile strength of pure and modified PAN membranes.
has fairly increased owing to the contribution of methylene group
from PF127 [19]. The characteristic peak at 2252 cm−1 is attributed
to C N stretching of nitrile groups [44]. The absorbance band
at 1600 cm−1 shifted to 1630 cm−1 due to the carbonyl stretch-
ing frequency present in the nano CaCO3 particles. A new peak
has emerged at 1453 cm−1 in addition due to the characteristic
vibration and out of plane pending vibration of C O (Carbonate)
group. The emergence of another new peak at 1050 cm−1 indicate
C O C stretching corresponding to ether groups which shows the
presence of PF127 molecules in the membrane matrix [21]. From
these findings it is evident that though some portion of PF127 is
washed away by water, some portion of Pluronic molecules were
still present in the membrane. The result of ATR-FTIR spectrum
confirms the successful incorporation of CaCO3 nanoparticles and
PF127 in the membrane matrix.
4.4. Mechanical strength analysis
A membrane with a good mechanical stability is a significant
feature for the practical application as well as for the long term
run. This is because, both mechanical property and stress experi-
encing by the pressure driven membranes are inter related. From
the presented Fig. 6, it is evident that the tensile strength of the
composite membranes was increased substantially with increase
in dosage of CaCO3 from 0.25 wt% to 0.75 wt% in the casting solu-
tion [32]. This must be owing to the strong interfacial adhesion
between polymeric chains and nano CaCO3 particles because of
the large interfacial area between the nanoparticles. It is apparent
that the enhancement of tensile strength is due to the good dis-
persion of nanoparticle into the membrane matrix and there was
no agglomeration. For instance, the decrease in strength would be
the indication of agglomeration of nanoparticles on the membrane
[45]. Agglomeration of nanoparticles on the membrane matrix hin-
ders the stress encountered on membrane and eventually ends in
lower tensile strength [46].
Comparatively, PAN membranes with Pluronic F127 as additive
possessed very low tensile strength of 1.635 Mpa. This might be
due to the enhanced macrovoid formation of membrane as well as
the lack of intermolecular adhesion between polymeric chain and
PF127 [21]. The stress − strain results implies a good dispersion of
CaCO3 nanoparticles at 0.75 wt%. Another possible reason is that,
some of the nanoparticles should have fixed within the pore walls
of membrane which can be noticed in membrane cross sectional
SEM pictures.
153
Fig. 7. TGA curves of PAN(MA ), PAN/PF127(M0 ), PAN/PF127/.25 wt% CaCO3 (M1 ) and
PAN/PF127/.75 wt% CaCO3 (M3 ) membranes.
4.5. Thermal gravimetric analysis (TGA)
Thermogravimetric analysis provides quantitative information
regarding the moisture and volatile substance present in the given
compound. The information regarding weight loss and thermal
break down assists in finding out the degradation mechanism as
well as the stability of polymeric backbone. The thermal curves
of pure PAN, PAN/PF127 and PAN/PF127/CaCO3 membranes are
shown in Fig. 7.
On thermal treatment, PAN undergoes cyclization due to the
intramolecular reaction of nitrile groups. For pure PAN, the thermal
degradation started at around 300 ◦ C. The weight loss occurred at
this point was due to the pyrolytic reactions. This phenomenon has
occurred in four steps. In the first stage, there was no mass loss
upto 277◦ C. Cyclization reaction occurs in this step and it did not
show any significant effect on weight change [47]. As a result, the
weight remains unchanged. In the second stage between 277◦ C
and 314◦ C, weight loss was due to the gradual release of volatile
gases such as HCN, NH3 , CH3 CN due to the nitrile oligomerisation.
In the third stage between 314 ◦ C and 463 ◦ C, a marginal weight
loss was observed which is attributed to the partial evaporation
of HCN & NH3 [48]. The fourth stage is associated with thermal
degradation reaction of polymer. In the fourth stage, there was a
steady decrease from 463 ◦ C to 788 ◦ C was observed that indicates
the complete evaporation of polymer [49].
TGA curve of hybrid membranes loaded with CaCO3 nanoparti-
cle illustrates that in the first stage decomposition started at 304 ◦ C
corresponding to the minimum loading. For the M3 membrane
with maximum loading of CaCO3 nanoparticle, it was observed
that degradation temperature shifted to 333 ◦ C. It is evident that
modified membranes were thermally stable than pristine PAN
membrane since the decomposition temperature shifted to higher
temperatures. For pure PAN membrane (MA ) the residual weight
was about 38%, then for M0, it was about 46% and for M1 it was
49%. It was observed that the residual weight has increased for M3
membranes for about 67% which was the maximum comparing to
other modified membranes. From Fig. 7, it is clear that thermal sta-
bility of M3 membrane is much higher compared to pristine PAN
membrane. This must be due to two factors: 1) The strong adhesion
of CaCO3 nanopaticles with polymeric chains and 2) Homogeneous
dispersion of nanoparicles.
154 J.S.B. Melbiah et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 516 (2017) 147–160
Fig. 8. SEM images of the cross-section morphologies of pure PAN (MA ), PAN/PF127(M0 ), PAN/PF127/.25 wt% CaCO3 (M1 ) and PAN/PF127/.75 wt% CaCO3 (M3 ).
4.6. Analysis of morphology of membranes
The cross sectional morphology of the prepared membranes was
examined to predict the membrane properties such as selectivity
and permeability. The SEM images are depicted in Fig. 8. A gen-
eral asymmetric structure of the typical UF membranes with the
dense skin top layer integrated to a porous substrate underneath
skin extended towards bottom can be seen in all the prepared
membranes. During phase inversion step, the polymer precipita-
tion occurring on immersing into coagulation bath is controlled
by kinetic and thermodynamic property which in turn influences
the morphological structure of membrane. On immersion, the out
diffusion of solvent from casting solution and in diffusion of non-
solvent makes the polymer thermodynamically unstable that leads
to demixing, diminishing free energy of mixing [50]
In this case, during phase inversion process, thermodynamic
stability must have altered in either ways. Owing to the intrin-
sic hydrophilic nature, a major part of PF127 added would have
extracted into coagulation bath enabling a quick migration of
nonsolvent (water) into those spaces to form macroviods. The
increase in hydrophilic units in membrane matrix creates more
channels favoring the diffusion of nonsolvent [51] The appearance
of macrovoids can be seen in PAN/PF127 (M0 ) membrane in Fig. 8.
Similar effect has been reported in the literature [19,22,52]
On the other hand, the addition of CaCO3 nanoparticle along
with PF127 increased the viscosity and acted together by sup-
pressing the overall diffusion between the components kinetically
[33,53]. In general, the higher viscosity enables out diffusion of sol-
vent from casting solution rather than indiffusion of nonsolvent
that may lead to the reduction of wider macrovoids to narrow fin-
ger like smaller pores. The enhanced viscosity on addition of CaCO3
hindered the mobility of polymeric chain and eventually resulted
in porous substructure with lot of inter connected pores. Thereby,
water permeability enhanced remarkably, deducting mass transfer
resistance [33,49,54]. These factors evidences that the addition of
nanoparticles has altered the cross sectional morphology by alter-
ing inner pore structure.
Finding the surface roughness of membrane is another impor-
tant parameter to identify the hydrophilic/hydrophobic nature of
membrane. The 3 dimensional AFM images of pure and hybrid
membrane is shown in Fig. 9. Roughness values reveal that PAN
with additive PF127 membrane is rougher compared to the pristine
PAN membrane. This must be due to the surface segregation of PEO
segments and the presence of bigger sized pores at the membrane
surface [51]. It can be noted that M3 membrane exhibited a higher
rougher value than the other membranes. This must be because of
the tightly packed polymer chains in the skin layer with more num-
ber of pores. The rougher surface could hold the water for long time
enabling an increase in water permeability [55,56]. These results
are in good agreement with obtained SEM results. SEM images and
AFM images revealed a remarkable change in membrane morphol-
ogy on modification which was found as more porous with higher
interconnectivity between the pores.
4.7. Wetting property of membranes
Hydrophilicity/hydrophobicity is an important parameter to
ensure the antifouling property of membrane which can be deter-
mined by measuring the water contact angle. The corresponding
change in water contact angle with respect to addition of PF127
and CaC03 nanoparticles is shown in Table 3.
 J.S.B. Melbiah et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 516 (2017) 147–160 155

Fig. 9. AFM micrographs of PAN (MA ), PAN/PF127(M0 ), PAN/PF127/.25 wt% CaCO3 (M1 ) and PAN/PF127/.75 wt% CaCO3 (M3 )membranes.

Table 3
Roughness parameter, Contact Angle, Work of Adhesion, and Spreading Coefficient, Surface Free Energy and Interfacial Free Energy values calculated for pure and modified
PAN membranes.

Membrane Ra (nm) Contact Angle (␪) Work of Spreading Surface free Interfacial free
adhesion,Wa coefficient, Sc, energy, ␥sv (mN/m) energy, ␥sl (mN/m)
(mN/m) (mN/m)

MA 41.82 76.2 89.17 −54.81 28.69 11.5

M0 70.39 60.1 107.89 −36.11 40.85 4.96
M1 65.87 71.6 94.73 −49.27 32.5 9.77
M2 71.93 46.8 121.29 −22.72 51.5 2.22
M3 77.1 20.0 139.65 −4.34 68.1 0.34

Fig. 10. Water contact angle measurements and work of adhesion for the pure and modified PAN membranes.

The pristine PAN membrane showed a water contact angle
of about 76.2◦ whereas for M3 , WCA went down to 20◦ for the
membrane M3, showing remarkable increase in hydrophilicity (see
Fig. 10). The significant decrement in contact angle from 76.2◦ to 20◦
ensures significant increase in flux as the intrinsic hydrophilicity of
membrane surface imparts a deep influence in permeation prop-
erty of membranes. The strong interaction of water molecules and
hydroxyl groups present in the membrane surface facilitated water
permeability in modified membranes with PF127 and nano CaCO3
[28]. It is well known that permeability of the membrane is influ-
enced by the combined effect of the morphology and hydrophilicity
[57]. Moreover, the high wetting property associated with mem-
brane surface is the key aspect for oil repulsion. The two factors that
influenced membrane hydrophilicity here are: 1) The high surface
free energy associated with CaCO3 nanoparticles that fairly tends
to form a hydration layer on their surface [56,58] and 2) The self
156 J.S.B. Melbiah et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 516 (2017) 147–160
Fig. 11. Time-dependent flux for pure PAN, PAN/Pluronic F127 and
PAN/PF127/CaCO3 membranes during ultrafiltration process. The ultrafiltra-
tion process includes the following steps: pure water ultrafiltration (0–6) h,
oil/water emulsion ultrafiltration (6–9) h, hydraulic washing (not shown), pure
water flux measurement of the cleaned membranes (9–14) h, oil/water emulsion
ultrafiltration (14–16) h, again SDS cleaning of membranes (not shown) and pure
water flux measurement of after cleaning with SDS solution (16–20) h.
assembly behavior of PEO chains that imparts excellent membrane
hydrophilicity [59].
From the observed contact angle values, the calculated values
for various surface parameters, such as surface free energy (␥sv ),
interfacial free energy (␥sl ), work of adhesion (Wa), and spreading
coefficient (Sc ) are depicted in Table 3.
In the case of pure PAN membrane MA , the surface free
energy was 28.69 mN/m and it is increased to 68.1 mN/m for the
PAN/PF127 hybrid membranes at maximum loading of nanoparti-
cle, M3 . The interfacial free energy ␥sl of MA membrane was 11.5
mN/m and it decremented to 0.34 mN/m for the membrane, M3
indicating high hydrophilicity. Work of adhesion, Wa defines the
interactive forces between the liquid and membrane surface. The
work of adhesion value has increased from 89.17 mN/m for MA to
139.65 mN/m for M3 . This increase in work of adhesion infers the
increase in adhesive force which in turn indicates the increase in
wetting property of the corresponding membrane. The spreading
coefficient values become less negative for M3 membrane. These
results endow a good increase in wettability.
Variations in percentage of porosity for pure membranes
and PAN/PF127 and PAN/PF127/CaCO3 membranes are shown in
Table 2. The minimum porosity value of 73.4% was found for pure
PAN membranes whereas, on adding PF127 the porosity increased
upto 81.5% [19]. On addition of nano CaCO3 to PAN/PF127 mem-
branes, high porosity of 85.8% was obtained at 0.75 wt% of CaCO3
which evidenced for the high wetting property of membrane [54].
4.8. UF performance
All the prepared membranes were tested for its efficiency by car-
rying out UF experiments with pure water and oil-water emulsion
and the antifouling ability of each membrane was predicted.
Initially, compacting the membrane for 1 h at a pressure of 60 psi
makes the membrane pores reoriented to specific geometrical
structure by deducting void volume and promoting a denser struc-
ture respectively. On compaction, the trace of solvents retained
within the pores will also be washed away. The time dependent
flux for pure water and emulsion is depicted in Fig. 11. The pure
water flux of pristine PAN membrane was found to be 191 L/m2 h.
On progressive addition of CaCO3 nanoparticle along with 1 wt% of
PF127, flux was substantially raised upto 343 L/m2 h (see Fig. 14).
This significant increase in water flux is attributed to the intrinsic
hydrophilic nature of PF127 and CaCO3 presented in the mem-
brane matrix. The additives increased the hydrophilic sites at
the membrane surface thereby enhancing hydrogen bonding. The
mechanism of action of nano CaCO3 and PF127 in PAN membrane
is shown in Fig. 12. The carbonate is flanked between the imine
and a hydroxyl bearing Pluronic acid. Both these groups essentially
impart hydrophilicity to the formed hybrid membranes. The strong
interaction of hydroxyl and ether group with water through hydro-
gen bonding increased hydrophilicity as increase in CaCO3 dosage
and enhanced permittivity. Not only that, the increase in number
of pores at membrane surface played a role here [33]. This can be
explained as follows.
During the filtration of oil-water emulsion mixture, the percent-
age of rejection with respect to time was analyzed and recorded at
regular intervals. The percentage of rejection of oil droplets with
respect to time is depicted in Fig. 13. It can be noted that 85% −
90% of oil droplets were removed in the first one hour of UF pro-
cess. This is because, the intrinsic hydrophilic nature of membranes
facilitated the formation of structured hydration layer that weak-
ened the contact between membrane surface and oil droplets [60].
Not only that, sieving mechanism also played a crucial role here. On
the contrary, in the meantime, there is a possibility of continuous
deposition of oil droplets due to higher flux. The deposition of oil
molecules should have reached equilibrium in sequential operation
owing to the rigorous stirring and eventually resulted in a steady
flux rate. This happens because, as time proceeds, the surfactant
layer surrounded by oil droplets tend to break partially, thereby
small oil droplets tend to coalesce making as bigger oil droplets
spreading out onto the membrane surface to form a surface layer
thus decreases the contact between water and membrane surface
[61]. From the time flux graph in Fig. 13, it can be observed that, the
pure water flux of PAN/PF127(M0 ) was little more when compared
with PAN/PF127membrane (M1 ) with 0.25 wt% of CaCO3 nanoparti-
cle. This should be due to the bigger membrane pore size of M0 than
M1 . At the same time, the percentage of rejection of oil molecules
was found to be lesser for M0 when compared with CaCO3 loaded
membranes. This is because of the migration of some of submi-
cron sized oil droplets through its bigger sized pore channels. In
this view, the higher flux as well as the highest oil rejection, 98%
achieved by M3 membrane must be through the combined effect
of hydrophilicity together with large number of small pores on
membrane surface.ie., compact hydration layer thus formed on the
porous rougher surface should have trapped water for a long time
exhibiting highest repulsion of oil molecules in the case of M3 mem-
brane [56]. From these findings, it is evident that increase in number
of pores has great influence on the separation performance.
4.9. Cleaning the oil fouled membranes with water
The time dependent flux of pure water after water wash fol-
lowed by flux taken on oil-water separation and pure water flux
taken after SDS wash is depicted in Fig. 11. FRR, DRr , DRirr and
DRT values were calculated after hydraulic washing and after SDS
washing which is displayed in Figs. 15 and 16. After hydraulic wash-
ing, the FRR value of the membranes was found to be increasing
in ascending order of 62.83(MA ) < 76.92 (M0 ) < 81.72 (M1 ) < 86.93
(M2 ) < 90.67 (M3 ). From this, it is inferred that oil foulants were easy
to sweep away in a simple water wash in the case of CaCO3 loaded
membranes indicating good antifouling property showing minimal
residence of oil droplets at the membrane surface. DRirr value was
found to be greater than DRr for all the membranes reveals that
fouling is mostly reversible. The membrane with maximum dosage
of 0.75 wt% of CaCO3 exhibited higher FRR and low DRT value which
 J.S.B. Melbiah et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 516 (2017) 147–160
Fig. 12. Proposed mechanism of action of nano CaCO3 and PF127 in PAN membrane.
is likely attributed to the presence of hydrated layer at membrane
surface as well as more number of pores.
4.10. Cleaning the oil fouled membranes with SDS solution
It can be observed in Fig. 16 that after washing with SDS, all
the membranes regained more than 90% of initial pure water flux
pertaining a good reliability and antifouling property. On the other
hand, the higher DRr value obtained for pristine PAN membrane
evidenced the residence of oil molecules at membrane surface
owing to the strong hydrophobic interaction of oil foulants on
membrane surface. After SDS washing, the membrane M3 , with
highest dosage of CaCO3 exhibited excellent antifouling perfor-
mance with higher FRR value and low DRr than on water cleaning.
From these findings, it is evident that PAN/PF127 membrane with
maximum dosage of CaCO3 nanoparticle is reliable enough for long
term run.
157
A comprehensive comparison of the performance of polymeric
membranes incorporated with organic/inorganic hydrophilic addi-
tives prepared by the phase inversion and this work has been shown
in Table 4. Research on modifying the polymeric membranes to
improve surface hydrophilicity in order to reduce fouling and to
increase the performance of membrane in oil/water separation
has been carried out using macromolecular polymeric additives
like PEG [63], PVP [64] and Triblock copolymers [53,61,62]. Recent
works are also focused on incorporation of nanomaterials like TiO2
[65], SiO2 [26,66], MWCNT [67], ZrO2 [67], Bentonite [26], HAO
[28] into the polymer matrix to address the above concerns. The
hydroxyl group present in these hydrophilic nanomaterials inter-
acts with surrounding water molecule to build a compact hydration
layer at the membrane water interface which effectively hinders
the non-specific adsorption of contaminants present in the feed
pollutants onto the membrane surface. These researchers have
focused on modifying PVDF, PSF & PES membranes for recovery
of water from oil-water emulsions. In our work, we have investi-
158 J.S.B. Melbiah et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 516 (2017) 147–160

Table 4
A comprehensive comparison of the performance of polymeric membranes incorporated with organic/inorganic hydrophilic additives prepared by the phase inversion.

Membrane Concentration Oil/water Pure water Feed FRR Change in Rejection Ref.
of oil/water emulsion flux flux Pressure (%) Water Contact (%)
emulsion (g/L) (L/m2 h) (L/m2 h) (Bar) Angle (◦ )

PES-PF127 0.9 ∼82.98 132 1 93.3 66.8–30 100 [62]

PSF-PEG 0.9 130 139 1 95 80–20 99.9 [63]
PVDF-PVP 0.2 345 554 3 93 65.6–30 95 [64]
PVDF-(PAUBA-b-PS-b-PAUBA) 1.0 60.5 360 2 77 80–73 99.5 [53]
PES-P(PEG-grad-TFOA)m 1.0 114.3 135.2 1 99.5 81–89 99.7 [61]
PES-TiO2 3.0 16.45 28 1.5 – 65–0 99 [65]
PSF-Bentonite 0.2 92 152 1 – 84–73 90 [26]
PSF-SiO2 0.2 94 98 1 – 84–62 90 [26]
PSF-HAO 1.0 191.08 1194 1 67 74–10 100 [28]
PES-[SiO2 -g-(PDMAEMA-co-PDMAPS)] 0.9 79.83 172.30 1 84.3 84.5–65 100 [66]
PVDF-ZrO2 -MWCNT 1.0 145 322.9 1.5 90 84.2–59.9 95 [67]
PAN-PF127-CaCO3 1.0 161 343 2 97.67 76.2–20 98 This work

Fig. 13. Percentage of rejection of oil with respect to filtration time. Fig. 15. Summary of the corresponding FRR, DRt, DRr, and DRir values of pure and
modified PAN membranes (cleaning the fouled membranes with water).

Fig. 14. Pure water flux profile of pure PAN and modified PAN membranes.

gated the performance of PAN membrane for the same application.
The nano CaCO3 has been determined as a cost effective nanomate-
rial which mitigates the fouling on membrane surface effectively.
The synergistic effect of macromolecular amphiphilic PF127 and
the nanoparticle CaCO3 can effectively prolong the life of the pre-
pared membranes and hence holds a great potential to be further
investigated commercially for oil-water emulsion separation.
Fig. 16. Summary of the corresponding FRR, DRt, DRr, and DRir values of pure and
modified PAN membranes (cleaning the fouled membranes with SDS solution).
5. Conclusion
In this study, PAN/PF127/CaCO3 hybrid membranes with highly
hydrophilic surface property was developed to resist oil fouling
for separating oil-water emulsion mixtures via. phase inversion
 J.S.B. Melbiah et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 516 (2017) 147–160
technique. The incorporation of amphibilic copolymer, PF127 and
inorganic nano CaCO3 particles into PAN membrane matrix resulted
in significant enhancement of membrane surface hydrophilicity
which led to the significant increase of pure water flux as well
as antifouling property. Comparing membrane performance, best
results were obtained for M3 membrane upon addition of the high-
est quantity of nanoparticle (.75 wt %). M3 membrane showed as
high as 90% flux recovery after a simple water wash, that evidenced
for its excellent antifouling property. The enhanced hydophilic-
ity enabled the compact hydration layer formation and trapped
water for a long time on its porous rougher surface which led to
low oil adhesion on membrane. Moreover, membrane properties
such as thermal stability, mechanical strength, porosity, rejection
were found to increase on increase in dosage of CaCO3 nanoparti-
cle in PAN/PF127 membrane matrix. These results indicate that the
addition of PF127 and nano CaCO3 to PAN membrane provides an
applicable way to improve the membrane properties so that it can
be employed for the efficient separation of emulsion droplet below
10 ␮m.
Acknowledgments
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
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