Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 157–169

Contents lists available at ScienceDirect

Chemical Engineering Research and Design

journal homepage: www.elsevier.com/locate/cherd

Improved permeation, separation and antifouling

performance of customized polyacrylonitrile
ultrafiltration membranes

J.S. Beril Melbiah a , Noel Jacob Kaleekkal b , D. Nithya Rabekkal a , D. Rana c ,

A. Nagendran d , D. Mohan a,∗
a Membrane Laboratory, Department of Chemical Engineering, Anna University, Chennai 600025, India
b Membrane Separation Group, Department of Chemical Engineering, National Institute of Technology Calicut
(NITC), Kozhikode, Kerala, India
c Department of Chemical and Biological Engineering, University of Ottawa, 161 Louis Pasteur St., Ottawa, ON K1N

6N5, Canada
d Polymeric Materials Research Lab, PG & Research Department of Chemistry, Alagappa Government Arts College,

Karaikudi 630 003, India

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

Article history: Tailored polyacrylonitrile (PAN) ultrafiltration (UF) membranes are fabricated with Pluronic-
Received 9 February 2020 F127 and polyethylene glycol phosphate decorated calcium carbonate (PGP-CaCO3 ) additives
Received in revised form 23 March with the aim of high water permeation, macromolecular rejection and antifouling proper-
2020 ties. The nanoscale CaCO3 synthesis is carried out via a single step carbonization route using
Accepted 14 April 2020 PGP as a hydrophilic modifier to introduce hydroxyl groups onto its surface. The topogra-
Available online 27 April 2020 phies of the nanoparticles are investigated using X-ray diffraction (XRD) and transmission
electron microscopy (TEM). PAN/PGP-CaCO3 mixed matrix membranes (MMMs) are fabri-
Keywords: cated via phase inversion method and examined by attenuated total reflectance-Fourier
Ultrafiltration membrane infra-red spectroscopy (ATR-FTIR), mechanical stability, thermo-gravimetric analysis (TGA)
Antifouling and scanning electron microscopy (SEM) to explore the changes in membrane properties
Polyacrylonitrile due to the well-dispersed PGP-CaCO3 in the PAN membrane matrix. The UF performance of
CaCO3 nanoparticles the membranes is investigated in terms of pure water flux, macromolecular rejection and
Pluronic F127 antifouling property. The fouling resistance of membranes is assessed using bovine serum
albumin (BSA) and humic acid (HA) as model foulants. The membrane loaded with 0.75 wt.%
(M3 ) of PGP-CaCO3 manifested increased wettability with reduced surface free energy lead-
ing to a higher pure water flux of 366 L/m2 h. M3 also displayed a rejection of 93.9% for BSA
and 93.2% for HA. The success of the modification can be confirmed as the membrane M3
exhibited lower flux decline and displayed a flux recovery ratio of 90.98% during HA filtra-
tion. The results demonstrated the potential use of PAN/PGP-CaCO3 membranes in water
treatment.
© 2020 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction

In recent years, the cost to treat and reuse water has

emerged as one of the crucial global challenges to humans.
∗
Corresponding author. In response to the increasing demand for useable water,
E-mail address: mohantarun@gmail.com (D. Mohan). the research and development of sustainable water purifica-
https://doi.org/10.1016/j.cherd.2020.04.014
0263-8762/© 2020 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
158 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 157–169
tion technologies are evolving. In recent decades, membrane
technology has been regarded as a suitable substitute to
conventional methodologies due to its ability to produce
pathogen-free and low turbid water from natural supplies
as well as industrial effluents (Baker, 2012). Nevertheless,
membrane fouling is an encumbrance to the large scale imple-
mentation of low-pressure membrane systems. This could
be explained by the adsorption of filtered components on
the membrane surface which easily plugs the membrane
pores thus increasing resistance to the filtration process.
Therefore, the development of a more versatile and tai-
lored fouling-resistant membrane is required (Guo et al.,
2012). An extensive feasible strategy to diminish membrane
fouling is the fabrication of highly hydrophilic surfaces pos-
sessing antifouling property. The hydrophilic polar groups
at the membrane surface fasten a large number of water
molecules and produce a dense organized water layer that
could effectively retard solute-membrane interactions (Wang
et al., 2017; Mockel et al., 1999). Techniques to embed
hydrophilic groups over polymeric membrane surfaces- sur-
face coating, thin-film composite (TFC) membranes, grafting,
UV-irradiation, etc., have been investigated in detail. How-
ever, these methods require the use of corrosive chemicals,
which comprises of complex reactions (Khajouei et al., 2019).
Alternatively, bulk modification of membranes made through
simple mixing of distinct nanomaterials could amplify the
inherent membrane characteristics such as water permeation,
selectivity, antifouling ability while maintaining the phys-
ical stability and chemical durability (Rana and Matsuura,
2010).
Even though the hydrophilic additives like
poly(vinylpyrrolidone) (PVP), poly(ethylene glycol) (PEG),
improves membrane hydrophilicity, they tend to leach out
during prolonged operation due to their low compatibility
with the hydrophobic base polymer (Lafrenière et al., 1987).
PF127, an amphiphilic, low-cost, low molecular weight poly-
mer, bearing a hydrophobic PPO group linked to hydrophilic
PEO groups has been proven to be a better membrane mod-
ifier as well as a suitable pore-forming agent (Susanto and
Ulbricht, 2009; Zhao et al., 2008). The hydrophobic backbone
of PF127 ensures better compatibility with the base polymer
and the hydrophilic chains improve the surface wettability of
the membranes. The macrovoids formation has pronounced
improvement in the water permeability however they dimin-
ish the mechanical stability which reduces the membrane
lifetime (Liu et al., 2012; Loh and Wang, 2012). At the same
time, membranes incorporated nanoscale inorganic particles
possessing quantum effects and high aspect ratio have
gained much interest of late. Introduction of a broad class
of hydrophilic inorganic nanoscale particles such as titania
(Pandiyan et al., 2018), silver (Sri Abirami Saraswathi et al.,
2019a), bentonite (Ahmad et al., 2018), boehmite(Farjami et al.,
2019), magnesium oxide (Arumugham et al., 2016), graphene
oxide (Jiang et al., 2019), hydrous aluminium oxide (Gohari
et al., 2015), salicylate alumoxane (Mokhtari et al., 2017), zinc
oxide (Rabiee et al., 2015), carbon nanotube (Ayyaru et al.,
2019), silicon dioxide (Ghandashtani et al., 2015), copper
oxide (Nasrollahi et al., 2019), and polycitrate-alumoxane
(Pirsaheb et al., 2019) have significantly improved mem-
brane hydrophilicity which in turn enhanced the antifouling
remarkably.
These mixed matrix membranes (MMMs), however,
encounter the problem of uneven distribution of the nanoscale
materials within its matrix. In order to minimize its sur-
face free energy, the nanoparticles tend to agglomerate which
reduces its dispersion and integration with the base poly-
mer matrix (Kango et al., 2013; Rajaeian et al., 2015). This
agglomeration also lowers the active sites required for the
interactions between the nanoparticle and surrounding poly-
mer, creating defects (Yang et al., 2006). Surface modification
of the nanomaterials can solve this problem, thus increasing
the active sites required for the effective interactions with the
surrounding polymer which enhances several desired mem-
brane aspects-improved mechanical/thermal stability, greater
hydrophilicity, higher permeation rate, desired rejection, etc.
(Deshmukh et al., 2010; Vatanpour et al., 2014; Rahimpour
et al., 2012; Qiu et al., 2009; Peyravi et al., 2014; Sri Abirami
Saraswathi et al., 2019b; Farjami et al., 2020).
Recent reports on PAN MMMs have indicated their suit-
ability for various water treatment applications. To address
some of the above-mentioned problems, Liu et al. prepared
amino-functionalized SiO2 and TiO2 nanoparticles to improve
their distribution within the PAN membrane matrix, which
in turn, enhanced the membrane hydrophilicity, porosity,
mean pore size, as well as its antifouling performance. The
modified PAN membrane exhibited pure water flux 44 times
greater than that of the pristine PAN membrane (Liu et al.,
2019). Tripathi et al. employed polydopamine modified silica
nanoparticles to enhance the water permeability of the PAN
MMMs (Tripathi et al., 2016). Hu et al. employed tetraethyl
orthosilicate to tune the pore size distribution of the PAN
membrane and to enhance its hydrophilicity with greater BSA
rejection of approximately 100% (Hu et al., 2018). Moreover, in
a recent work of Bahmani et al. prepared MMMs using PAN and
hematite (␣-Fe2 O3 ) nanoparticles and found to be suitable for
the removal of nitrate ions from aqueous solutions (Bahmani
et al., 2018). Zahid et al. prepared PAN/goethite MMMs which
displayed a 49.1% removal of Cu(II) heavy metal ions from
aqueous solutions while improving the pure water permeabil-
ity to 285 L/m2 h (Soghra et al., 2019).
In this work nanoscale CaCO3 is used owing to its ease of
fabrication, relative non-toxicity, mechanical/thermal stabil-
ity and antibacterial characteristics (Abdolmohammadi et al.,
2012; Ataee et al., 2011). The surface of the nano calcium car-
bonate is modified using polyethylene glycol phosphate (PGP)
in a one-step approach to ensure uniform dispersion of the
nanoparticle within the membrane matrix. Moreover, the PGP
modified nanoparticles possess a large number of hydroxyl
groups which hydrates the membrane surface quickly. There-
fore, this work is mainly focused on to illustrating the effect of
surface-modified and unmodified CaCO3 nanoparticles in the
PAN UF membrane.
Herein, a highly hydrophilic membrane is fabricated by
embedding PGP decorated nanoscale CaCO3 nanoparticles
into PAN matrix via the phase inversion technique. To the
best of our knowledge, no reports are available on PGP deco-
rated CaCO3 to prepare PAN/F127 based UF membranes. Firstly,
the synthesis of PGP decorated CaCO3 nanoparticle is carried
out to improve the nanoparticle distribution within the mem-
brane matrix. The change in cross-sectional morphology of
the prepared membranes is analyzed through a scanning elec-
tron microscope (SEM). The inclusion of PGP decorated CaCO3
nanoparticle and PF127 on membrane layer is confirmed by
means of ATR-FTIR analysis. The effect of PGP decorated
CaCO3 nanoparticles on the properties of PAN membranes is
studied based on pure water flux, surface wettability, removal
of BSA and HA.
 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 157–169 159

2. Experimental Table 1 – Composition of PAN/PF127/PGP-CaCO3 hybrid

membranes.
2.1. Materials Membrane Blend composition Solvent (wt.%)

Polymer and additive (wt.%) NMP

Calcium oxide (CaO) is purchased from Merck, India Ltd is
used as the precursor. Polyethylene glycol (PEG) 1000 Da and PAN PF127 PGP-CaCO3 CaCO3
polyphosphoric acid are purchased from Merck for the syn-
MP 9 0 0.00 0.00 91.00
thesis of polyethylene glycol phosphate (PGP). Commercial Mx 9 1 0.00 0.00 90.00
grade PAN (150,000 g/mol) is kindly supplied by Technorbital, M1 9 1 0.25 0.00 89.75
Uttar Pradesh, India. Pluronic PF127 (12,600 g/mol) and Tween M2 9 1 0.50 0.00 89.50
80 are purchased from Sigma Aldrich. AR grade N-methyl-2- M3 9 1 0.75 0.00 89.25
pyrrolidone (NMP) from SRL Chemicals Ltd., India is sieved M4 9 1 0.00 0.75 89.25
using molecular sieves (4 Å) in order to eliminate moisture and
stored in dry conditions prior to use. For antifouling studies, ation ( = 1.5406 Å) and scanned in a 2 scale from 20◦ to 80◦
bovine serum albumin (BSA, 66.5 kDa) and humic acid (HA) at a scan rate of 2◦ per min. Debye–Scherrer Equation (Monshi
are procured from SRL Chemicals Ltd. India. The surfactant, et al., 2012) is applied to compute the crystallite size of the
sodium dodecyl sulfate (SDS) is obtained from Glaxo India Ltd. prepared nanoparticles which is as follows:
Distilled water is employed throughout the experiments for
the preparation of casting bath as well as for the UF studies. K
L= (1)
ˇ cos 
2.2. Preparation of PGP
where L is the mean size of the crystallite (nm); K is the crys-
tallite shape factor;  is the X-ray wavelength; ˇ is the FWHM
A mixture of 50 g of poly (ethylene glycol) 1000 (PEG 1000) and
(full width at half max);  is the Bragg angle (◦ ).
5.6 g polyphosphoric acid was introduced into a 100 mL three-
necked flask. After constant stirring at room temperature for
2.4.3. High resolution-transmission electron microscope
0.5 h, and then the temperature was increased to 90 ◦ C and
(HR-TEM)
maintained for 3 h. Subsequently, the mixture was removed
The structural morphology of the synthesized CaCO3 and PGP
from the flask and allowed to cool to room temperature in air
decorated CaCO3 nanoscale particles are evaluated using a
to obtain PGP.
transmission electron microscope system with JEM-3010 TEM
(Joel Ltd, Tokyo, Japan) operating at a high voltage of 200 kV.
2.3. Synthesis of pristine and PGP decorated CaCO3
nanoparticles 2.5. Fabrication of membranes

PGP-CaCO3 was prepared as reported previously in literature
(Sambudil et al., 2014; Chen et al., 2010). 68 g of CaO was
digested in 1000 mL distilled water at 100 ◦ C to form Ca(OH)2
slurry. After 12 h, the slurry was filtered through a 200 meshes
sieve. PGP of 5 g was added into 150 mL slurry with vigorous
stirring. Then the carbonization reaction monitored by pH
value of the slurry was carried out at 19 ◦ C. The gas mixed
by CO2 and N2 was bubbled into the mixture. The synthesis
of CaCO3 nanoparticle was done by precipitation technique.
The solution ‘A’ was prepared by dissolving. 1 M of Na2 CO3 in
deionised water along with 0.2 M of NaOH and 0.18 M of CaCl2 .
A solution ‘B’ containing 0.1 M of Ca(NO3 )2 was also prepared.
Subsequently, solution ‘B’ was added drop wise to the solution
‘A’ under vigorous stirring at determined agitation speed. The
solution mixture thus obtained was kept at constant mechani-
cal stirring for about 1 h. The end product was centrifuged and
dried to obtain CaCO3 nanoparticles.
2.4. Characterization of nanoparticles
2.4.1. FTIR
The FTIR spectrum for the both pristine and PGP modified
CaCO3 nanoparticles are recorded using KBr pellet method
with a spectrometer (Spectrum RXI, Perkin Elmer) in the range
of 400–4000 cm−1 .
2.4.2. XRD
The wide-angle X-ray diffraction (WAXD) pattern of the
nanoparticles is recorded on a Bruker AXS D8 Advance X-ray
diffractometer. The X-ray source is produced by a Cu K␣ radi-
The mixed matrix flat sheet membranes are prepared using
the phase inversion technique. A homogeneous dope solution
is obtained by mechanically stirring PAN (9 wt%) and PF127
(1 wt%) in NMP (solvent) at a constant rate for 20 h at 35 ◦ C.
The synthesized nanoparticle is added in the same method as
described in the previous study (Beril Melbiah et al., 2017). Prior
to casting, the resultant homogenous solution is de-aerated
overnight to eliminate air bubbles completely. Then the dope
solution is cast onto a finely polished glass substrate using
a casting knife with a 0.22 mm specific gap height. The glass
plate is then gently transferred into a gelation bath containing
water (Non-Solvent) and kept for 12 h at room temperature to
ensure complete phase separation. The casting solution com-
position for each membrane is given in Table 1.
2.6. Characterization of the mixed matrix membranes
2.6.1. Determination of molecular weight cut off (MWCO)
and mean pore size
A series of PEG solution (2 wt.%) of increasing molecular
weight is employed to compute MWCO of each of the prepared
membranes. The concentration of feed, and permeate is ana-
lyzed using TOC (Shimadzu, TOC–VCPH ). The solute rejection
(SR) percentage is determined by using the following formula:
 
Cp
SR(%) = 1− × 100 (2)
Cf
where Cf is the concentration of feed; Cp is the concentration
of permeate.
160 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 157–169
The average pore size of the membranes is computed from
the acquired MWCO values. The molecular weight of the PEG
solution displayed more than 90% of solute rejection is consid-
ered as the MWCO, M of the respective membrane. The pore
radius of each membrane is evaluated by using the formula
which is as follows (Mockel et al., 1999):
 The contact angle is determined from the captured water
r = (0.0262 nm) M (g/mol) − 0.03 nm (3)
2.6.2. Analysis of the chemical structure
FTIR Spectra of the membranes are examined using attenu-
ated total reflectance (ATR) technique with a spectrophotome-
ter (Spectrum RXI, Perkin Elmer) in the range of 400–4000 cm−1 .
2.6.3. Analysis of tensile strength
The tensile strength of the membranes is evaluated through
ASTM D8882 standard with an Instron 3369 analyzer with an
elongation rate of 10 mm/min. Excess water is mopped from
equal-sized samples before testing using tissue paper. Three
measurements were averaged for 3 samples and reported for
accuracy.
2.6.4. Thermal analysis
The analysis for the thermal behaviour of membranes is car-
ried out by thermos-gravimetric analysis (TGA) using through
Universal V4.5A TA DTG analyzer under Nitrogen atmosphere.
The heating rate of the samples is maintained at 20 ◦ C/min and
samples are heated from room temperature up to 800 ◦ C.
2.6.5. Morphological analysis
The prepared membranes are cut to equal sizes (1 cm × 1 cm)
and wiped carefully with a blotting paper to get rid of moisture.
Subsequently, dried samples are fractured in liquid nitrogen
for 30–60 s. The samples are then sputter-coated with gold
under vacuum to obtain electrically conducting samples. The
cross-sectional micrographs of the membranes are obtained at
an accelerating voltage of 15 kV using SEM-Cam scan MV2300
(Hitachi, Japan).
2.6.6. Porosity and equilibrium water content
The membrane porosity (ϕw ) is determined by the water
uptake capacity of membranes using the following expression:
W0 − W1
ϕW = × 100 (4)
W AL
where W0 , wet weight of membrane (g); W1 , dry weight of
membrane (g); w , the density of water (g/cm3 ); A, membrane-
active area (cm2 ); and L, membrane thickness (cm).
Equilibrium water content (EWC) is directly related to
porosity and hydrophilicity of the membrane. After soaking
the membrane samples of equal size in pure water for 24 h, the
membranes are removed out and mopped gently with blotting
paper to get rid of excess moisture and weighed carefully to
obtain the wet weight of the membrane (W0 ). Then, the dry
weight (W1 ) is estimated after drying the same membranes
for 48 h in a vacuum at 80 ◦ C. The water content is computed
by the following equation:
W0 − W1
EWC(%) = × 100 (5)
W0
2.6.7. Surface wettability
The wettability of the membranes is further confirmed by
the water contact angle (OCA 15EC, Data Physics, Germany)
measurements using the sessile drop technique. The mem-
brane samples cut to a requisite dimension of 3 cm × 3 cm
for analysis are wiped gently with blotting paper to remove
the presented moisture content. Using a Hamilton microliter
syringe, Milli-Q water is dropped onto the membrane surface
and the image is captured after 10 s.
drop images. Six such measurements from various locations
are made and averaged for the contact angle value of each
sample. From the measured contact angle values, the interfa-
cial free energy ( sl ), surface free energy ( sv ), work of adhesion
(Wa ) and spreading coefficient (Sc ) are computed using formu-
las follows:
sl = sv − 1v cos  (6)
Wa = (1 + cos )1v (7)
Sc = sv − sl − 1v (8)
where  lv is the interfacial surface tension of liquid and vapour
phase (72 mN/m at 25 ◦ C) and  is the contact angle measured.
2.7. Ultrafiltration performance evaluation of
membranes
2.7.1. BSA rejection
The BSA solution is prepared by dissolving 0.05 wt.% of BSA
in 0.5 M phosphate buffer saline (PBS) at pH = 7. The prepared
foulant solution (500 mg/L) is then filtered through each of the
prepared UF membranes at 2 bar and permeate is collected at
regular time intervals. The BSA present in permeate is quanti-
fied using UV absorbance at 280 nm using Libra S50, Biochrom
Ltd., Cambridge, England.
2.7.2. HA rejection
HA, a natural organic matter (NOM) is dissolved in de-ionized
water to prepare a feed solution having a concentration of
500 mg/L and adjusted to a pH of 6.0. UF experiment is done
using HA solution and permeate is collected at regular inter-
vals. The concentration of organic carbon of permeate is
quantified using a total organic carbon analyzer (Shimadzu,
TOC-V CPH). The rejection (%) of HA from the feed solution is
calculated using Eq. (2):
2.7.3. Flux studies and fouling analysis
The antifouling characteristics and separation potential of
the fabricated membranes are assessed by accomplishing UF
experiments using Amicon (Model 800, USA), batch type dead-
end UF cell with a volumetric size of 350 mL to mimic the
maximum fouling conditions. The effective membrane area
of the UF cell is 45.38 cm2 which is further attached to a feed
solution reservoir (Jayalakshmi et al., 2012). Filtration cell is
stirred with a Teflon-coated magnetic paddle fitted inside the
cell in order to limit concentration polarization. The filtration
proceeded in a stepwise manner as follows: Initially, the mem-
branes are pre-compacted by applying a specified pressure of
4 bar for an hour using distilled water as feed. The operating
pressure is fixed at 2 bar, permeate is collected and quantified
at fixed intervals until attaining a stable flux (0–6 h). The pure
water flux (Jw ) is computed using the following expression.
Q
Jw = (9)
A.t
 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 157–169 161

phase is confirmed due to the characteristic absorption bands

observed at 717 and 875 cm−1 (Islam et al., 2013) and the vibra-
tion band around 1079 cm−1 is assigned to the characteristic
symmetric carbonate stretching of aragonite phase. The PGP-
CaCO3 displayed a broad absorption peak at 3448 cm−1 which
can be ascribed to the stretching vibration of OH groups indi-
cating the presence of water molecules on the PGP decorated
CaCO3 nanoparticle (Mishra et al., 2011). The absorption peaks
present at 2864 and 2930 cm−1 are correspond to the asym-
metric and symmetric C H stretches of the alkyl (methyl,
ethyl) groups present in the PGP (Wang et al., 2010). In addi-
tion, the emergence of a peak in PGP decorated CaCO3 around
1025 cm−1 is due to the stretching vibration absorption of P O
(Gao et al., 2011). Herein PGP may have interacted with Ca2+
via an ionic bond. The aforementioned results suggested that
PGP molecules remained strongly associated with the CaCO3
nanoparticles.

3.2. HR-TEM analysis of nanoparticles

HR-TEM images of pure and PGP decorated nano CaCO3 are

presented in Fig. 2a and b. The obtained micrograph clearly
Fig. 1 – FT-IR spectra of pure and surface modified shows that the nanoparticles are predominantly cuboidal
nanoparticles. (Gumfekar et al., 2011). The average particle size of the CaCO3
nanoparticles ranged between 72 and 95 nm whereas the mod-
where Q is the volume of water permeated (L); t is the water ified nanoparticles are in the range of 96–105 nm. The increase
permeation time (h); A is the effective area of membrane (m2 ). in particle size is an indication of the complete encapsulation
The solution reservoir is refilled with two kinds of model of the CaCO3 with PGP (Roy et al., 2016). The visible increase
foulant solutions individually such as protein (500 mg/L, BSA in surface roughness also indicates the chemical deposition
in PBS) and NOM (500 mg/L, HA in DI water) successively for of PGP on the surface of CaCO3 . Moreover, it was noted that
fouling mechanism studies. The flux for the model foulant there was a reduction in the agglomeration of the PGP dec-
feed solutions is also computed as mentioned above and orated nanoparticles which could be explained by the steric
recorded as Jp (protein) and Jh (HA) (6–10 h). After cleaning the repulsion effect.
membranes with DI water, the pure water flux is determined
for another 5 h to find out the reversibility of fouling. The fluxes 3.3. XRD of nanoparticles
thus obtained are termed as Jw1 (BSA) and Jw2 (HA) (10–15 h).
The efficiency of the membrane in terms of antifouling prop- The XRD patterns obtained displayed the phase composi-
erty is evaluated by finding flux recovery ratio (FRR) and total tion and crystalline structure of the prepared nanoparticles
flux decline (DRT ) using the equation given as follows: (Fig. 2c). The XRD reflection patterns confirmed that the pre-
J  pared CaCO3 crystals were in the most thermodynamically
Flux Recovery Ratio, FRR =
w1
× 100 (10) stable calcite form. The peaks observed at 2 = 23.04◦ , 29.45◦ ,
Jw 36.0◦ , 43.06◦ , and 48.0◦ have been indexed for (012), (104), (110),
J − Jp
 (202), and (116) planes respectively and found to match with
w1
Reversible Flux Decline, DRr = × 100 (11) the JCPDS #47-1743 standard (Zhao et al., 2016). The absence of
Jw
aragonite, vaterite or uncertain phases and the lack of unde-
J − J  fined peaks signify the excellent purity of prepared nanoscale
w w1
Irreversible Flux Decline, DRirr = × 100 (12) CaCO3 (Blanco et al., 2011; Chen et al., 2012). The average crys-
Jw
tallite size determined from the Scherrer equation is 81 nm
J − J  for pure CaCO3 and 95 nm for PGP-CaCO3 . These results are
w p
Total flux decline, DRT = × 100 (13)
Jw consistent with the crystallite sizes determined from the TEM
images. Furthermore, the similarity in the surface treatment
Similarly, FRR and DRT values on filtering HA solutions are did not alter the crystal structure of the nanoparticle.
computed. The sum of reversible and irreversible flux decline
gives the total flux decline (DRT ) value. 3.4. ATR-FTIR spectra of membranes

3. Results and discussion
3.1. FTIR of synthesized nanoparticles
The FT-IR spectra obtained for the pure and PGP decorated
CaCO3 nanoparticles (PGP-CaCO3 ) are plotted as Fig. 1. The
pure and the PGP decorated CaCO3 display peaks at 1411 cm−1
which can be attributed to the stretching frequency C O (car-
bonate asymmetric stretching). The formation of the calcite
The incorporation of PGP decorated CaCO3 nanoparticles into
the PAN membranes is seen to alter its chemical compo-
sition as evidenced by the ATR-FTIR spectra (Fig. 3). The
absorption peak associated with nitrile ( CN stretching) of the
base polymer, PAN, is observed at 2243 cm−1 for all the pre-
pared membranes. The peak at 1050 cm−1 is present in all the
PF-127 incorporated membranes as it accounted for C O C
stretching corresponding to ether groups present in the PF-
127 (Zhi et al., 2015; Sri Abirami Saraswathi et al., 2018a). The
162 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 157–169

Fig. 2 – TEM micrographs pure CaCO3 (a) and PGP decorated CaCO3 (b); and X-ray diffraction pattern of raw CaCO3 and
PGP-CaCO3 nanoparticles (c).

absorption band at 3368 cm−1 is ascribed to the OH stretch-

ing vibrations of the hydroxyl groups present on the modified
nanoparticles. A gradual increase in the intensity of this char-
acteristic broad peak can be recognized as the increase of
PGP-CaCO3 on the membrane surface. An increase in the
intensity of the absorption peaks at ∼2863 and ∼2929 cm−1 is
attributed to the alkyl groups of the PGP. The mixed matrix
membranes also exhibited a peak at 1725 cm−1 due to the
presence of carboxylic ester linkages. Membrane incorporated
with pure CaCO3 (M4 ) is devoid of the prominent peaks (2863,
2929 and 1725 cm−1 ) associated with the PGP. The obtained
ATR-FTIR spectrum of hybrid membranes confirmed that (i)
the surface of CaCO3 is successfully modified by PGP and (ii)
the modified nanoparticle is successfully incorporated in the
membrane matrix (Sri Abirami Saraswathi et al., 2018b,c).

3.5. Tensile strength

Fig. 3 – ATR-FTIR spectra of membranes.
High tensile strength is desired for long-term utilization of
the membranes in any pressure-driven processes. The results
of the mechanical analysis presented in Fig. 4a showed an
increase in tensile strength for the MMMs up to a loading
of 0.75 wt.% after which a slight decline is observed. The
 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 157–169
Fig. 4 – Tensile strength (a) and TGA curves (b) of MP , MX , M1 , M3 and M4 membranes.
improvement in the tensile strength of the MMMs could be due
to factors such as the homogenous distribution of nanopar-
ticle and good compatibility with the base membrane. The
membrane Mx displayed the least tensile strength of 1.635 MPa
which must be due to a large number of macrovoids present as
evident from the SEM images. Moreover, the membranes with
the PGP decorated CaCO3 possessed greater tensile strength
than the membrane with pure CaCO3 (M4 ) for the same load-
ing ratio. This further confirms the strong interfacial adhesion
between the modified nanoparticles and the base polymer,
owing to good dispersion of PGP-CaCO3 nanoparticles espe-
cially at 0.75 wt.% (M3 ) loading (Bao and Tjong, 2007; Rahimi
et al., 2015).
3.6. Thermo-gravimetric analysis (TGA)
All the membranes exhibited only negligible weight loss up to
300 ◦ C. The thermal degradation of the pure PAN membrane
at ∼300 ◦ C is due to the intramolecular cyclization reaction
of the nitrile groups (Fig. 4b) (Ouyang et al., 2008). Thermal
decomposition of M3 began at 398 ◦ C with the increasing
concentration of PGP-CaCO3. It is apparent that modified
nanoparticles impregnated membranes for instance M3 and
M4 are much more thermally stable than the pristine PAN
membrane. For the pristine PAN membrane (MP ), the resid-
ual weight obtained is about 38%, at 800 ◦ C which is lowest as
compared to the nanoparticle incorporated membranes. For
the membrane MX , the residual weight is ∼46%, M4 displayed
64% and the greatest residual weight is for M3 (70%). It is quite
evident that the thermal stability of membrane M3 , containing
modified nanoparticle is greater than the membrane contain-
ing pure nanoparticles. The enhancement in thermal stability
is mainly due to the presence of a large number of polar func-
tional groups of PGP which further aids in further linking
between the base membrane matrixes. Moreover, the other
reason is due to the (i) strong adherence between PGP-CaCO3
nanoparticles and polymeric chains; and (ii) the homogeneous
distribution of surface-modified nanoparticles.
3.7. Cross-sectional morphology of membranes
The cross-sectional morphological structure of the prepared
membranes is observed using SEM (Fig. 5). The cross-sectional
SEM micrographs of all the membranes displayed clear asym-
metric morphological structure with a top sieving skin layer,
a spongy layer beneath and a finger-like spongy layer project-
ing towards the bottom with fully open pores at the bottom
(Kanagaraj et al., 2016). Generally, during the membrane fab-
rication by the phase inversion process, the polymer solution
163
precipitation occurring in the gelation bath is dominated by
the thermodynamics of the system as well as the solution
kinetics. These two forces play an integral role in determining
the membrane structure (Guillen et al., 2011). In the case of Mx ,
the presence of PF-127 having a high affinity for water reduces
the thermodynamic stability of the dope solution when intro-
duced into the water bath and an accelerated exchange of
solvent or non-solvent occurs leading to faster phase separa-
tion. The polymeric molecules tend to form clusters in order
to reduce the interaction with the non-solvent and create
macrostructures also observed (Kim et al., 2001).
Moreover, it is clear that the addition of the modified
nanoparticles has manipulated the membrane morphology as
well. In the MMMs, the number of finger-like slender channels
increased compared to the PAN control membrane. This can
be explained as follows: The inclusion of small amounts of
PGP-CaCO3 into base polymer increased the viscosity of dope
solution thereby suppressing the rate of solvent/non-solvent
exchange and thus delay in demixing make a porous struc-
ture. On the other hand, the strong polar interactions between
hydroxyl moieties of free PGP present and surrounding water
molecules favours faster penetration of water molecules due
to the strong hydrogen bonding. These two factors in unison
lead to the growth of a large number of small-pores which
further coalesce each other to interconnect between the top
and bottom of the membrane matrix which is in agreement
with earlier reports. At the maximum loading of 0.75 wt. %
of PGP-CaCO3 (M3 ), the membranes exhibited more elongated
finger-like formation than others (Beril Melbiah et al., 2019;
Manickam et al., 2014).
3.8. Membrane wetting property
3.8.1. Porosity, water content and pore size of membranes
The effect of functionalized nano CaCO3 on the porosity and
mean pore size is listed in Table 2. The porosity of the pure PAN
membrane is determined to be 74.3% and the porosities of the
MMMs increased on incorporating PGP decorated CaCO3 . The
membrane containing 0.75 wt % PGP-CaCO3 had the greatest
porosity of 86.7% and is in accordance with the water content
values reported in Table 2. The calculated membrane pore size
is observed to increase with the nanoparticle concentration up
to 0.75 wt.%. These obtained results are in congruence with the
water contact angle and pure water flux explained in further
sections.
3.8.2. Water contact angle (WCA)
Water contact angle (WCA) values measured through
goniometer renders the information pertaining to the
164 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 157–169

Fig. 5 – Cross sectional morphology of MP , MX , M1 , M3 and M4 membranes.

Table 2 – Porosity, water content, MWCO and mean pore size of the prepared mixed matrix membranes.
Membrane code Porosity (%) Water content (%) MWCO (kDa) Mean pore size (Å)

MP 74.3 67.8 25 41.1

Mx 81.5 73.0 70 69.0
M1 82.2 72.4 45 55.2
M2 83.6 74.1 70 69.0
M3 86.7 77.9 70 69.0
M4 85.8 76.2 40 52.1

Table 3 – Surface wettability and wetting parameters of membranes.

Membrane code Contact angle Work of Spreading Surface free Interfacial
() ± 0.5 adhesion, Wa coefficient, Sc energy,  sv free energy,
(mN/m) (mN/m) (mN/m)  sl (mN/m)

MP 76.2 89.17 −54.82 41.0 23.77

Mx 60.1 107.89 −36.11 49.8 13.91
M1 58.0 110.15 −33.84 50.5 12.34
M2 36.8 129.65 −14.35 61.0 3.35
M3 13.0 142.15 −2.15 70.0 0.15
M4 20.0 139.65 −4.34 68.1 0.44

hydrophilic nature of the prepared membrane surfaces. The
intrinsic wetting nature of the membrane called ‘hydrophilic-
ity’ positively impacts the water permeation and anti-fouling
propensity of the membranes (Farjami et al., 2019; Zhu et al.,
2014). As seen in Fig. 6, the PAN membrane, in the absence
of any of the additives displayed the greatest contact angle
of 76.2 ± 0.5 (Table 3) which indicates its low surface wettabil-
ity. On the addition of Pluronic onto the PAN membrane (Mx ),
the water contact angle is lowered. As the PGP-CaCO3 con-
tent in the membrane increased to 0.75 wt.%, the measured
water contact angle is remarkably low (13◦ ) which confirms
the improvement in surface hydrophilicity. The water con-
tact angle results are consistent with the ATR-FTIR spectra.
The improvement in the surface wetting could be explained
as follows: (i) The hydrophilic PGP coated nano CaCO3 tend to
migrate spontaneously to the membrane surface to reduce the
surface free energy during phase inversion process and (ii) The
strong polar interactions (H-bonding) between the abundant
hydroxyl groups of PGP and the surrounding water molecules.
The optimized loading rates and the uniform dispersion
of PGP-CaCO3 in the membrane matrix enable the oxygen-
containing functional groups to be oriented towards the
membrane surface imparting hydrophilicity and in turn mem-
brane permeability. An increase beyond the optimal loading
leads to an uneven distribution which can diminish the active
functional groups on the membrane surface (Xu et al., 2014;
Zhang et al., 2013; Baig et al., 2016). The role of the PGP decora-
tion is highlighted by the lower contact angle of M3 compared
to M4 and this is due to the abundant OH groups present.
The details of the measurements such as interfacial energy,
surface energy, work of adhesion are provided the insight
about wetting property of the prepared membranes and the
 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 157–169
Fig. 6 – Water contact angle measurements and work of
adhesion of membranes.
values are shown in Table 3. For the pristine PAN membrane
MP , the surface free energy is found to be 41.0 mN/m and
reached and 70 mN/m for the hybrid membrane, M3 which
contains 0.75 wt.% of PGP-CaCO3 . The interfacial free energy
( sl ) of the MP membrane is found to be 23.77 mN/m and it is
lowered to 0.15 mN/m for M3 signifying higher hydrophilic-
ity. Work of adhesion, Wa explicates the interactive forces
between the membrane surface and the wetting liquid. Wa
value improved from 89.17 mN/m for MP to 142.15 mN/m for
M3 as shown in Table 3. This increase in the work of adhesion
further inferred the increase in adhesive force which eventu-
ally evidenced for the enhancement in the wetting nature of
the modified membrane. Moreover, the spreading coefficient
(Sc ) values become more positive for modified membranes
with increasing concentration of nanoparticles. These results
revealed a good increase in the wettability of modified mem-
branes.
3.9. Ultrafiltration performance and fouling analysis
3.9.1. Effect of modified nanoparticle/membrane in pure
water fluxes
The pure water permeation test is carried out at 2 bar and
the results reported are an average of 3 runs. The prominent
increase in pure water flux from 191 to 366 L/m2 h for Mx and
M3 respectively is attributed to the increase in the membrane
pores with greater connectivity as well as the improvement in
surface hydrophilicity. The presence of abundant OH groups
bonds with the surrounding water molecules consequently
Fig. 7 – Time-dependent flux for pure PAN and hybrid membranes during BSA (a) and HA (b) filtration.
165
results in higher water permeation of M3 . It is also noted that
the pure water flux of M3 was greater than M4 which confirms
the enhancement in hydrophilicity due to the abundant OH
groups. As explained in the earlier section, the reason for the
intensification of the hydrophilicity is owing to the existence
of an abundant number of OH groups on the introduction of
PGP modified nanoparticles.
3.9.2. Anti-fouling performance of the prepared
membranes
The pure water flux, solution flux and pure water flux after
membrane cleaning is plotted for BSA and HA and shown
in Fig. 7a and b. The pure PAN membrane displayed dras-
tic flux decline when tested with the BSA solution for 4 h.
This could be explained by the low hydrophilicity of the
PAN membrane surface which permits the protein adsorption
at the membrane-water interface. The hydrophobic protein
tends to disintegrate the weakly patterned water layers eas-
ily and interacts much faster with the membrane surface.
The membrane M1 showed better performance than the pure
PAN membrane however, there is an observable flux decline
as the concentration of hydrophilic moieties on the mem-
brane surface was low. The protein adsorption on M1 restricts
the mobility of polymeric chain by compressing hydrophilic
polymeric brushes (PGP) rendering entropy loss (Sri Abirami
Saraswathi et al., 2020; Yu et al., 2013). The stable BSA solu-
tion flux is calculated to be 176 L/m2 h after 60 min for M3 and
is the highest observed while the membrane MP exhibited the
lowest flux of 91 L/m2 h. The reason could be explained as fol-
lows: the membrane M3 is enriched with polar OH groups at
the surface that can bind easily with the surrounding water
molecules through hydrogen bonding. This densely packed
hydration layer that is thus formed stretches into the sur-
rounding aqueous environment providing a steric hindrance
for the BSA molecules (Zhao et al., 2012). The BSA reten-
tion of modified membranes reached 93.9% because of the
increase in hydrophilicity and appropriate pore size as shown
in Table 4.
The antifouling parameters DRr, DRirr and FRR are cal-
culated for all the prepared membranes during BSA protein
separation and shown in Fig. 8a. The pure PAN membrane
suffered maximum flux decline and exhibited the lowest
FRR of 76.44% implying irreversible fouling of the hydropho-
bic surface. M3 membrane displayed maximum flux recovery
(90.71%) indicating the surface fouling is reversible. The irre-
versible fouling ratio (DRirr) decreased from 23.56% for pure
PAN membrane to 9.29% for M3 showing an improvement
in surface fouling resistance due to the presence of the PGP
166 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 157–169

Table 4 – BSA protein and HA permeate flux and rejection performance of the membranes.
Membrane code Flux (L/m2 h) Rejection (%)

Jw1 Jp Jw2

BSA HA BSA HA BSA HA BSA HA

MP 191 191 91 71 146 141 89.1 88.0

Mx 286 286 138 115 241 220 90.1 89.0
M1 311 311 149 139 260 261 92.0 91.3
M2 347 347 166 151 309 309 93.1 92.4
M3 366 366 176 164 332 333 93.9 93.2
M4 343 343 172 145 317 296 92.9 91.1

Table 5 – Comparison of the UF performance results of the present work with other PAN UF membranes.
Membrane Feed pressure Flux on Pure water flux Change in FRR (%) Rejection (%) Ref.
(bar) filtration of (L/m2 h) water contact
model foulant angle (◦ )
solution
(L/m2 h)

PAN-amino- 1 200 (BSA) 234.3 68.4–61.7◦ 78.4 99.3 (Liu et al., 2019)
functionalized
SiO2
PAN-amino- 1 100 (BSA) 1204.6 68.4–53.2◦ 85.6 95.1 (Liu et al., 2019)
functionalized
TiO2
PAN–orthosilicate 1 28 (BSA) 58.7 61.8–41.7◦ 90.3 ≈100 (Hu et al., 2018)
(TEOS)
PAN-PF127 3.45 156 (BSA) 391 76.2–36.8◦ 93.42 (BSA) 95 (BSA) (Beril Melbiah
et al., 2019)
165 83.8 (HA) 90 (HA)
PAN-PF127-PGP- 2 176 (BSA) 366 76.2–13◦ 90.71 (BSA) 93.9 (BSA) In this work
CaCO3
164 (HA) 90.98 (HA) 93.2 (HA)

Fig. 8 – Fouling analysis of membranes during BSA (a) and HA (b) filtration.

coated nanomaterials. Moreover, it is apparent that PGP could
be used as a surface modifying agent to enhance the perfor-
mance of nanoparticle.
The HA solution flux profile is similar to the protein solu-
tion as shown in Fig. 8b, however, the behaviour of the HA
molecules is entirely different from BSA protein molecules
due to its structure (Zularisam et al., 2006). In general, the
hydrophobic nature of aliphatic and aromatic moieties which
is present in the HA molecules tend to adsorb on hydropho-
bic membrane surfaces. As seen in the flux profile of HA
filtration, the fluxes of all membranes are high at the initial
stage of filtration. After 60 min of the run, the flux value has
dropped down to procure a constant flow. The pure PAN mem-
branes displayed poor anti-fouling resistance which leads to
the adsorption of the organic foulants on the membrane pores
as well as interior walls and the flux declined to 71 L/m2 h
after 4 h of filtration as shown in Table 4. The incorporation
of the PGP decorated CaCO3 improved the permeate flux to
164 L/m2 h and had a high rejection of 93.2% for membrane
M3 .
The FRR value for the reusability of themembrane has
increased by up to 90.98% for the modified PAN membrane
(M3 ). In contrast, the pristine one, MP had the lowest FRR value
of 73.82%. As the concentration of PGP-CaCO3 is increased,
the irreversible fouling (DRirr) decreased to as low as 9.02%
for M3. The reversibility of fouling of the PGP decorated
nanoparticle incorporated membranes is not only due to its
improved surface hydrophilicity but also due to larger pore
openings. From these results, it could be concluded that the
modified MMMs possess superior anti-fouling ability with
excellent water permeation and high rejection of contami-
nants.
 Chemical Engineering Research and Design 1 5 9 ( 2 0 2 0 ) 157–169
The comparison of present results with the results of other
similar investigations in literature is provided as Table 5. It
shows clearly, the PAN-PF127-PGP-CaCO3 UF membrane found
to be suitable for potential use in water treatment.
4. Conclusions
PGP decorated CaCO3 nanoparticles are found to effective
in tuning the pore size and performance of PAN/PF127 UF
membranes. The decoration of CaCO3 with PGP notably
enhanced dispersion and compatibility with the PAN matrix
and also found to substantially increase membrane per-
formance in terms of water contact angles. The abundant
hydroxyl groups present in the membrane matrix imparted
more hydrophilicity on the surface providing extra OH group
which improved the pure water flux from 191 L/m2 h (MP )
to 366 L/m2 h (M3 ) with a higher BSA rejection of 93.9%.
The permeability of MMMs is dependent on the amount
of PGP-CaCO3 in the casting solution. The impregnation of
surface-treated nanoparticle presented notably enhanced dis-
persion and compatibility with the base polymeric matrix.
The cross-sectional images revealed that the incorporation
of PGP modified produced membranes with interconnected
pores. The optimal membrane performance is accomplished
on the addition of 0.75 wt% of PGP-CaCO3 nanoparticles to
PF127/PAN membranes in terms of membrane stability, per-
meation, BSA/HA rejection and antifouling properties.
Conflict of interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
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