Ceramics International 47 (2021) 25883–25894

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Synthesis and characterization of superoleophobic fumed alumina

nanocomposite coated via the sol-gel process onto ceramic-based hollow
fibre membrane for oil-water separation
Yusuf Olabode Raji a, b, Mohd Hafiz Dzarfan Othman a, *, Nik Abdul Hadi Sapiaa Md Nordin c,
Mohd Ridhwan Adam a, Khairul Anwar Mohd Said a, d, Ahmed Fauzi Ismail a,
Mukhlis A. Rahman a, Juhana Jaafar a, Twibi Mohamed Farag a, Sabeer Abdulhamid Alftessi a
a
Advanced Membrane Technology Research Centre (AMTEC), School of Chemical and Energy Engineering, Universiti Teknologi Malaysia, 81310 UTM, Johor Bahru,
Johor, Malaysia
b
Department of Chemical Engineering, Abubakar Tafawa Balewa University (ATBU), 0248, Bauchi, Nigeria
c
Department of Chemical Engineering, Universiti PETRONAS (UTP), 32610, Seri Iskandar, Perak, Malaysia
d
Department of Chemical Engineering and Energy Sustainability, Faculty of Engineering, Universiti Malaysia Sarawak, 94300, Kota Samarahan, Malaysia

A R T I C L E I N F O A B S T R A C T

Keywords: Oily wastewater treatment is a global challenge due to the substantial amount of effluent resulted from many
Superoleophobic industrial and domestic activities. To overcome the challenge of using existing treatment approach and fouling,
Perfluorooctanoate superoleophobic coatings were fabricated. In this study, a superoleophobic membrane surface was obtained
Sol-gel
using the sol-gel technique with perfluorooctanoate (PFO), poly (diallyl dimethylammonium chloride) (PDAD­
Stark membrane hollow fibre
Dip-coating
MAC), and nanoparticles as complex-polymer nanocomposites. The effects of coating cycles on the surface
Oil-water separation structure, chemical properties, surface chemistry, and oleophobicity of the surface were examined using field
emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), X-ray
diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and oil contact angle measurement. The results
showed that the coated layer successfully adhered to the substrate surface. However, the chemical stability with
respect to oil contact angle (OCA) revealed a decline at pH 7 and pH 9 and maintained stability at pH 3. Besides,
oil flux at 63.0 L/m2. h was achieved for PDADMAC-Al2O3/44 wt% PFO and the highest separation efficiency of
98% was obtained. Furthermore, the oil rejection decreases as the oil concentration increases from 1 to 3 g/L.
OCA of 155◦ was obtained after 5 coating cycles. Apart from mitigating substrate fouling, the superoleophobic
and superhydrophilic coating can be applied to a ceramic-based hollow fibre membrane and efficiently used for
the separation of oil from oily wastewater.

1. Introduction
Oily wastewater generated through various industrial activities has
become a global issue affecting human and aquatic lives. Conventional
approaches for the treatment and separation of oil from oily wastewater,
such as coagulation, floatation, gravity settling, and ultrasonic separa­
tion have been found to be ineffective mainly due to low separation
efficiency, complex process separation units, high energy cost and sec­
ondary pollution [1–5]. Membrane technology is one of the effective
methods for oil-water treatment because of its ease of operation, and the
clean technology that allows the reuse of permeates and low energy
consumption [6]. This technology does, however, have limitations when
it comes to long term usage, as fouling affects the integrity and stability
of the membrane surface. Oil adsorption on the membrane surface leads
to membrane fouling and consequently resulting in low separation ef­
ficiency and reduced water permeability [7]. The oil adsorption to the
membrane surface, the chemical affinity between the two phases re­
duces the surface tension and oil contact angle of the membrane,
resulting in a lower energy barrier for the oil and thereby allowing oil to
penetrate into the macrovoids structures of the membrane [5,8,9].
Materials with extreme wettability allow favourable interfacial
interaction between solid surface and oil droplets [5]. Recently, the

* Corresponding author.
E-mail address: hafiz@petroleum.utm.my (M.H.D. Othman).

https://doi.org/10.1016/j.ceramint.2021.05.319
Received 18 March 2021; Received in revised form 31 May 2021; Accepted 31 May 2021
Available online 11 June 2021
0272-8842/© 2021 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Y.O. Raji et al.
emergence of superoleophobic materials provides a new approach to
address the limitations of the available oily wastewater treatment ap­
proaches. This current approach helps to achieve oil-repellent coatings
by applying fluoroalkyl group and/or nanostructure with a composite
[10]. Superoleophobicity occurs when an oil droplet shows an extreme
surface contact angle greater than 150◦ with a slide angle lesser than
10◦ . This indicates the ability of the substrate surface to be highly
dewetted when in contact with liquid [11]. Despite its enormous ad­
vantages, there are still challenges in the development of super­
oleophobic membrane materials. Previous studies had developed and
focused on the extreme wettability of surfaces using interfacial materials
coated stainless steel mesh and cotton fibre [12–14]. The overwhelming
use of metallic based substrate can be attributed to its availability and
porous structure. However, it is prone to corrosion (which is chemically
unstable) [15]. Nevertheless, as majority of oil molecules are repelled
from the superoleophobic surface, oil with low surface tension can still
manage to wet the membrane surface leading to a build-up of foulant
and reductions in flux rates that, ultimately result in a decline in the
operation and the performance of the membrane [16–19]. The use of
hollow fibre ceramic membrane as a substrate coated with interfacial
materials for water reclamation in the oil and water separation has not
been reported in the literature. Few recent studies reported, only
focused on oil reclamation from oily wastewater using hollow fibre
ceramic membrane with coated interfacial materials [20–24]. Due to the
inherent nature of oils with low surface energy, the inner membrane
surface had been fouled by oils which are difficult to remove, which
resulted in another secondary contaminant during post-treatment. This
ultimately blocks and ruins the inner surface of the membrane.
To address the fouling, materials with low surface tension/energy
such as –CF3 group (fluoroalkyl surfactants) on the stark membrane
surface are preferable. Fluoroalkyl surfactants have been used for
extreme oil-repellence [12,14,25]. Findings indicate that the synthesis
of PDADMAC-PFO (PP) can be conducted using a sol-gel method [20,
26]. This has proven to be a simple and excellent way to obtain super­
oleophobic grafting with an extreme contact angle and chemical sta­
bility [27]. Although incorporating PP on a membrane would
significantly improve the oil rejection, the water permeation ability
would be disrupted by this oleophobic surfactant. Therefore, for reme­
dying this enigma, a hydrophilic group compatible with the PP should be
introduced, such as alumina. Combining PP with alumina would
assemble a unique chemical with a dual function; hydrophilic and
oleophobic. This modified P/alumina/P or PDADMAC-Al2O3/PFO
would exhibit unique properties that resemble a flip-flop mechanism.
The flip-flop mechanism referred to its dual function in which one end
(PP) could repel the oil while the others (alumina) allow water trans­
port. Hence, the introduction of PDADMAC-Al2O3/PFO on a membrane
surface would create a smart membrane that rejects oil but allow water
to permeate through.
Therefore, the objective of the present study was to synthesize a
complex polymer nanocomposite: sodium perfluorooctanoate (NaPFO),
poly (diallyl dimethylammonium chloride) (PDADMAC) and alumina
nanoparticle using sol-gel method and to apply it as a coating suspension
to enhance its distinct chemical structure and hierarchical surface
roughness. To evaluate the coated membrane, the effect of chemical
stability in terms of wettability property and coating parameter (coating
cycle) were studied. The result was also characterized in terms of
wettability properties.
2. Experimental
2.1. Materials
Stark membrane fabricated from our laboratory (Advanced Mem­
brane Technology Research Centre, Johor, Malaysia): thickness: 0.380
mm, internal diameter: 1.38 mm, outer diameter: 1.76 mm average pore
size: 2.99 μm and flexural strength: 126 MPa was first hydrolyzed in
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Ceramics International 47 (2021) 25883–25894
ethanol/water mixture (1:2) for 24 h to enhance the hydroxyl group
bonding on the stark membrane surface. Kaolin-based ceramic mem­
brane (substrate) preparation was performed in accordance with the
previous study; the stark membrane was fabricated using the phase
inversion technique, followed by the sintering process [24,28,29]. The
FESEM image of the cross-sectional surface of the membrane is shown in
Fig. 1.
2.2. Chemicals
Poly (diallyl dimethylammonium chloride) (PDADMAC, C8H16ClN,
97%, Sigma Aldrich) was used as a dispersion agent and viscosity
adjuster, while sodium perfluorooctanoate (C8F15O2Na, Alfa Aesar) was
employed to produce the oil repelling characteristics of the coating
membrane, while fumed alumina (Al2O3 nanoparticles, 99%, Acros
brand, Belgium) was used to achieve surface roughness. Besides, iso­
propyl alcohol (C2H5OH, 99.5%, Sigma-Aldrich) was used as a drying
agent, and hydrochloric acid (HCl, Merck) and sodium hydroxide
(NaOH, Merck) were used to prepare the solution acid and basic,
respectively. The materials were used without further purification.
2.3. Synthesis of PDADMAC-Al2O3/PFO
0.5 g of Al2O3 nanoparticles was ultrasonically dispersed into a so­
lution containing 0.2 g of PDADMAC in 5 mL of deionized water for a
period of 60 min. After that, 5 mL of PFO aqueous solution was added
dropwise under continuous stirring at room temperature for 30 min. The
final generated product was filtered and washed with deionized water
and dried for 24 h (Fig. 2a). The intercalation between oleophobic and
hydrophilic components was achieved using the reaction of NaPFO and
PDADMAC with fumed alumina nanoparticles in an aqueous solution
(Fig. 2b). The final product was denoted as PDADMAC-Al2O3/PFO
complex polymer.
2.4. Synthesis of PFO-PDADMAC
0.2 g of PDADMAC was dispersed in 5 mL of deionized water and the
solution was stirred for 30 min. Afterwards, 5 mL of PFO aqueous so­
lution was added dropwise under continuous stirring at room temper­
ature for another 30 min. The final product was filtered and washed with
deionized water and dried for 24 h (Fig. 3a). The chemical reaction
between the polyelectrolyte and fluorosurfactant is illustrated in Fig. 3b.
The final product was denoted as PDADMAC-PFO complex polymer.
2.5. Surface coating of Stark membrane (substrate) by dip-coating
technique
The two synthesized products (PDADMAC-PFO and PDADMAC-PFO/
Al2O3) were dispersed into ethanol (10 mL) under sonication as the
coating suspension. The resulting suspension was used as a coating
material into the stark membrane (substrate). Simple dip-coating, a cost-
effective and industrial-friendly method, was used to deposit the nano­
composites into the stark membranes. This was carried out by slowly
inserting the substrate into the coating suspension and quickly with­
drawing it. The stark membrane surface was left to dry at room tem­
perature for 2 h to allow the ethanol to evaporate completely. The stark
membrane surface was abrase with soft cotton pads and then washed in
a mixture of deionized water and ethanol (1:2) to enable hydroxyl group
formation on the stark membrane surface. Both ends of hollow fiber
stark ceramic membrane of about 10 cm in length were potted with
PTFE film tape, prior to vertical dip-coating of the membrane. The stark
membranes were dipped into the coating suspension at different coating
cycles (1–5 cycles). For each coated cycle, the stark membrane was dried
in an open-air to allow ethanol to completely evaporate. The same step
was repeated for other coating cycles. Upon retraction, the membrane
was dried for 24 h at room temperature.
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Fig. 1. FESEM images of the cross-sectional surface (a) and the outer surface of the stark hollow fibre ceramic membrane.

2.6. Membrane characterization at 2 bar as the recovery flux. The fouling resistance (FR) percentage was
used to determine the notch of the fouling process of stark membrane
The coated and uncoated membrane surface structures were probed coated with PDADMAC-Al2O3/22 wt% PFO and PDADMAC-Al2O3/44
using field scanning electron microscopy (FESEM, SU8020 Hitachi) at wt% PFO membrane using Eq. (2) [30,31]:
different magnifications. The crystallinity of stark membrane, stark Fouling resistance (FR) efficiency (%) was determined using Eq. (2).
membrane coated with PDADMAC-PFO, stark membrane coated with
PFwi − PFSS
PDADMAC-Al2O3/22 wt% PFO, and stark membrane coated with FR(%) = ( ) × 100 (2)
PFwi
PDADMAC-Al2O3/44 wt% PFO was examined using an X-ray diffrac­
tometer (XRD: Goniometer, smartlab). X-ray photoelectron spectroscopy where PFwi is the initial water flux (L/m2. h) and PFSS is the final water
(XPS: Kratos Axis Ultra) analysis was used to perform local surface flux (L/m2. h) at a steady-state flux.
composition and survey spectrum analysis with a molecular electron The oil rejection was determined using Eq. (3).
spectrometer using an A1Kα line excitation source on the PDADMAC-
Al2O3/PFO coated with 44 wt% PFO. Contact angle measurement was R=
Cf − CP
*100 % (3)
performed using a contact angle goniometer (OCA 15 EC, Dataphysics, Cf
Germany). The volume of the various liquids used in all measurements
was approximately 0.5 μL. The images and angles of oil and water where R is the oil rejection (%); Cp is the concentration of the permeate
droplets on the coated surface were captured and measured. (g/L) and Cf is the concentration of the feed (g/L).

3. Results and discussion

2.7. Membrane performance

3.1. Field scanning electron microscopy (FESEM)

A cross-flow filtration (CFF) system step-up was used to measure oil
separation and pure water flux performance of the coated membrane.
Fig. 4 compares the cross-sectional and outer surface morphology of
The olive oil concentration was also varied at 1, 2 and 3 g/L. The con­
stark membrane, stark membrane coated with PDADMAC-PFO, stark
centration was varied to establish, sufficient concentration that would
membrane coated with PDADMAC-Al2O3/22 wt% PFO and stark mem­
separate water from the emulsified oil. The emulsified oil/water was
brane coated with PDADMAC-Al2O3/44 wt% PFO. The stark membrane
prepared using olive oil, osmosis water, and sodium dodecyl sulfate
surface displays a distinctly smooth, compact and slate-like structure
(SDS) as a surfactant. The ratio of 1:9 of SDS to oil was used during the
that is very open and porous where macrovoids are present (Fig. 4 a1
preparation. The olive oil particle was analyzed by Anton Paar (Litesizer
and 4 a2). Upon simple dip-coating of the stark membrane with
500) while the concentration of feed and permeate were analyzed using
PDADMAC-PFO containing a high concentration of fluorinated alkyl
LAMBDA 1050 UV–vis spectrophotometer at a wavelength of 335 nm.
groups with complex polyelectrolyte groups, a rough surface with
The CFF system was operated at room temperature, while the pressure
numerous aggregates and a well-cemented, film-like surface was ob­
was varied at 1, 2 and 3 bar. After 20 min of stability, the water permeate
tained (Fig. 4 b2). The figure reveals a closed and less porous structure
was collected at an interval of 20 min and operated for 120 min. The oil
(macrovoids). The tight porous structure of the top-layer structure can
flux was then calculated using Eq. (1).
be attributed to the presence of polyelectrolytes, which destabilized the
V fluorinated alkyl groups. However, Fig. 4 (c1 and c2) show an apparent
Jw = (1)
A*Δt agglomeration of PFO adhering to the surface of the substrate. Fumed
Al2O3 nanoparticles were applied to intercalate with PFO, which formed
where Jw is pure water flux (L/m2. h), V is the volume of permeate
the basis for the rough hierarchical structures. The figure also reveals the
collected (L), A is the effective surface area of the coated membrane (m2)
presence of fluorinated compounds with a thinner surface (nano­
and Δt is the time interval of collecting permeate (h).
composite) and also, of note was the hierarchical roughness of the sur­
Experiment with model foulant (olive oil) was performed to estimate
face. This can be attributed to the deposition of Al2O3. Meanwhile, Fig. 4
the antifouling property of the membrane samples. The concentrations
(d1 and d2) show the hierarchical surface morphology of PDADMAC-
of foulants solution were 1 g/L, 2 g/L and 3 g/L. Prior to the antifouling
Al2O3/PFO on the dip-coated stark membrane. The roughness of the
experiment, the pure water flux, PFwi (L/m2. h) of the stark membrane
structures appeared as extended rhythmic lumps of a film-thin coated
was conducted at 2 bar. A cross-flow ultrafiltration test was performed
layer with unpronounced protrusions. The structures indicate no distinct
under the same pressure where the permeate was collected at 20 min for
porous structure (macrovoids). This pattern of hierarchical textured
2 h and a steady flux for the foulant was obtained over a period of 2 h.
surface morphology can be ascribed to the sparse deposition of fumed
After the 2 h filtration process, the membrane was cleaned with RO
alumina nanoparticles [14]. As a result, the PDADMAC-Al2O3/PFO
water and another pure water flux, PFSS (L/m2. h) was conducted for 2 h

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Fig. 2. (a) Schematic procedure for sol-gel preparation of synthetic PDADMAC-Al2O3/PFO complex polymer nanocomposites. (b) Chemical reaction scheme used for
the synthesis of PDADMAC-Al2O3/PFO.

coating on the stark membrane can easily experience surface wettability 3.2. Energy-dispersive X-ray spectroscopy (EDXS)
by water. Hence, PDADMAC-Al2O3/PFO stark membrane can tolerate
and display intermittent superoleophobic and superhydrophilic The chemical composition of the coating elements and the elemental
surfaces. analysis of the uncoated and coated layers are presented in Fig. 5a. The

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Fig. 3. (a) Schematic procedure for sol-gel preparation of synthetic PDADMAC-PFO complex polymer. (b) Chemical reaction scheme used for the synthesis of
PDADMAC-PFO.

Fig. 4. FESEM cross-sectional and outer surface images of: stark membrane (a1, a2), stark membrane coated with PDADMAC-PFO (b1, b2), stark membrane coated
with PDADMAC-Al2O3/22 wt% PFO (c1, c2) and stark membrane coated with PDADMAC-Al2O3/44 wt% PFO (d1,d2).

uncoated layer is the stark membrane while the coated layer was made
of three different layers; the first layer was the PDADMAC-PFO layer
while the PDADMAC-Al2O3/PFO formed the second layer after coating
with 22 wt% PFO; the third layer was the PDADMAC-Al2O3/PFO layer
coated with 44 wt% PFO. From the EDX micrographs of the substrate
illustrated in Fig. 5a, it can be seen that it mainly contained Al, Si, O, C,
Fe, and K as the major elemental components as expected. The presence
of silica and alumina in the substrate activated the crosslinking between
the substrate and the coating layer. The EDX of the coated PFO which
contained mainly of F, N, Al, Si, C and O is shown in Fig. 5b. The

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Fig. 5. EDX mapping and elemental composition of: stark membrane (a), stark membrane coated with PDADMAC-PFO (b), stark membrane coated with PDADMAC-
Al2O3/22 wt% PFO (c) and stark membrane coated with PDADMAC-Al2O3/44 wt% PFO (d).

presence of CF− on the substrate suggests the formation of fluorinated coated layer on the stark membrane and this has a significant influence
alkyl groups. Samples coated with 22 wt% PFO exhibited the highest on the coated surface in terms of its superoleophobicity and
presence of CF− group with loss of silica due to the deposition of fluo­ superhydrophilicity.
rinated alkyl group (Fig. 5c). Contrarily, the silica composition showed a
significant reduction from 11.4% to 0.2% due to the deposition of
3.3. X-ray diffraction (XRD) study
alumina nanocomposite on the stark membrane. Fig. 5d shows higher
fluorine (F) atoms content (10.4%) while aluminum (Al) showed an
The stark membrane and crystalline transition of PDADMAC-Al2O3/
increase from 23.8 to 26.8% possibly due to the disappearance of Si.
PFO nanocomposites were characterized by XRD to obtain insight into
Based on the EDX mapping, there was a successful deposition of the
the PFO’s fluorosurfactant adsorption of Al2O3 nanoparticles (Fig. 6).

Fig. 6. XRD patterns of the stark membrane, stark membrane coated with PDADMAC-PFO, stark membrane coated with PDADMAC-Al2O3/22 wt% PFO, and stark
membrane coated with PDADMAC-Al2O3/44 wt% PFO.

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From the XRD pattern of the stark membrane which represents the
kaolin membrane, the diffractions showed different peaks at 2θ =
10.82◦ , 14.22◦ , 19.72◦ , 26.8◦ , 28.54◦ , 40.26◦ , 47.68◦ , and 56.86◦ which
denote the mullite structure. High presence of mullite can be attributed
to the phase transformation from kaolinite to mullite at high sintering
temperature and also confirmed the presence of cristobalite in a scanty
amount. In other words, mullite is more predominant in the crystalline
structure with a significant intense peak compared to cristobalite. The
XRD diffraction pattern is in line with the previous studies [32,33], and
kaolinite JCPDS No.: 01-0890-6538. However, three coated membranes
showed similar patterns in their respective peaks. Moreover, the XRD
spectrum of coated membranes revealed a right shift in their structures
from crystalline to semi-crystalline as a result of intercalation of the thin
film of PDADMAC/PFO on the Al2O3 nanoparticle. The diffraction peaks
of Al2O3 in PDADMAC-Al2O3/PFO revealed dissimilarity with stark
membrane diffraction peaks, and that Al2O3 is well intercalated and
homogeneously dispersed onto the PDADMAC/PFO matrix. The com­
plex polyelectrolyte-fluorosurfactant polymer formation,
PDADMAC-PFO showed sharp and highly intense peaks. This can be
attributed to a change of crystallinity in the amorphous polymer. Less
intense diffraction peaks were observed at 2θ (3–15.28◦ , 18.24–23.56◦ ,
27.06–29.94◦ , 66.74–95.86◦ ). A similar trend of phase shift was
observed when the stark membrane was coated with PDADMAC-Al2O3
with 22 and 44 wt% PFO. This can be attributed to the rearrangement of
molecules present in the carboxylate hydrophilic head and the n-octyl
oleophobic tail of PFO [34–36]. The peak shifts to 2θ = 17.74◦ , corre­
sponding to the interlayer distance existing between the nanocomposites
and suggesting that PDADMAC/PFO chains have entered the interlayer
region of the nanoparticle [37].
3.4. X-ray photoelectron spectroscopy (XPS) study
High-resolution XPS was performed to probe the local surface
composition as well as the survey spectrum of superhydrophilicity and
superhydrophobicity of the stark membrane coated with PDAD­
MAC–Al2O3/PFO as displayed in Fig. 7a. The elemental composition was
found to include C, F, O, N, and Al. Similar results were also observed in
a study conducted by Yang et al. [14]. The results have shown that the
composites possessed a high presence of F atoms (42%). The positively
charged N2 in the PDADMAC compound was assigned as N 1s at peak
Fig. 7. XPS survey spectrum of the prepared (a) PDADMAC-Al2O3/PFO coated with 44 wt% PFO; high-resolution readings provided for: (b) Al 2p, (c) F 1s, (d) O 1s
and (e) C 1s spectrum.
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(406 eV). Also, high survey spectrum resolution Al 2p revealed the
presence of Al–O- (78 eV), while O 1s (Fig. 7d), showed different peaks
at Al2O3 (414.0 eV), C–O (403) and C–– O (395). On the other hand, C 1s
(Fig. 6e), revealed the presence of –CO– (74.0 eV), –COO– (66.0 eV),
–CF2- (69.0 eV), and –CF3- (70.0 eV). In addition, the probe for fluorine
atoms, as shown in Fig. 7c revealed F (693 eV). The results can further
describe the presence of PDADMAC-Al2O3/PFO, as an intercalated
composite on the stark membrane, demonstrating the hydrophilicity and
oleophobicity of the top surface of the membrane [12]. However, the
presence of Al2O3 as a hydrophilic material favours the water penetra­
tion of the membrane surface as it creates the necessary hierarchical
surface structures. Meanwhile, the presence of PFO enhances the oleo­
phobicity of the surface.
3.5. Surface wettability study
The obtained surface wettability was excellent due to the good
interaction between the polyelectrolytes of PDADMAC and the fluori­
nated groups of PFO. A high oil contact angle of 155◦ (shown in Fig. 8a)
was achieved; this showed an increase of 1–5 from the initial coating
cycle. The presence of the perfluoroalkyl group in the coated membrane
reduces the surface interaction with the oil due to its weak intermo­
lecular force. Similarly, the water contact angle was about 25◦ at the
initial surface droplet but became 5◦ after 10 min of penetration. This
implies that the PDADMAC-Al2O3/PFO coated surface on the stark
membrane can easily be wetted by water at about 0◦ and with olive oil
contact angle of 155◦ . Fig. 8b reveals the chemical stability of the coated
membrane at pH 3, 7 and 9; this result is suggestive of greater stability of
the coated surface in terms of OCA in an acid medium at pH 3, as no
considerable changes were observed in the oil contact angle values as
compared with pH 7 and 9. This can be attributed to the reduction in the
adsorption of anionic fluorosurfactant onto alumina nanoparticles as the
pH value is increased from 7 to 9 in the basic medium [38]. Hence,
superhydrophilicity and superoleophobicity can be easily obtained
through the simultaneous interaction between polyelectrolyte and
fluorinated composite compounds on the substrate after a simple
dip-coating process.
Y.O. Raji et al.
Fig. 8. The wetting process of a water droplet on the PDADMAC-Al2O3/PFO
coated with 44 wt% PFO coating. (a) The CA of an oil droplet on the PDAD­
MAC-Al2O3/PFO coated with 44 wt% PFO coating with respect to coating cycle.
(b) Chemical stability with respect to contact angle of oil.
3.6. Separation performance for oily wastewater
3.6.1. Oil flux test
Further studies were also performed on the oil flux of the uncoated
and coated membranes. From the comparison of the oil flux of the un­
coated and coated membranes shown in Fig. 9, the stark membrane
exhibited the highest oil flux at 120 L/m2. h, followed by PDADMAC-
Al2O3/22 wt% PFO-coated stark membrane at 87 L/m2. h, and the
PDADMAC-Al2O3/44 wt% PFO-coated stark membrane at 63 L/m2. h.
The least oil flux was observed for the membrane coated with
PDADMAC-PFO at 46 L/m2. h. This stark membrane phenomenon could
be due to the efficient packing of the ceramic particles in the membrane
structures [24,39] as seen in Fig. 4 (a2), which allowed the permeation
of liquid through the spaces of ceramic particles to improve its oil flux.
The use of the stark membrane coated with PDADMAC-PFO exhibited a
drastic decline in oil flux possibly due to the close-packed in the surface
structure of the membrane from the complex-polymer thin film of
PDADMAC-PFO since it is not possible to achieve molecular water
molecules rearrangement on time to allow water permeation through
the membrane [5].
Usage of the stark membrane coated with PDADMAC-Al2O3/22 wt%
PFO showed an increase in oil flux due to the presence of alumina
nanoparticles that improved the membrane surface roughness and
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Fig. 9. Oil flux of the stark membrane, stark membrane coated with
PDADMAC-PFO, stark membrane coated with PDADMAC-Al2O3/22 wt% PFO,
and stark membrane coated with PDADMAC-Al2O3/44 wt% PFO.
improved oil flux across the coated surface. The oil flux performance of
the stark membrane coated with PDADMAC-Al2O3/44 wt% PFO was low
due to the high presence of fluorinated group of PFO that delayed the
interaction of the coated layer with the substrate. Hence, it is clearly
shown that PFO improved the oil flux based on the trend in Fig. 9. The
mechanism of oil repelling by the membrane was based on two unique
mechanisms; each has different pathways but both explaining the oil
repelling effect displayed by the membrane [40]. The first mechanism
was the flip-flop mechanism, and this mechanism was driven by the
fluorinated group which in this study is the PFO. Hence, the increase in
PFO loadings has directly reduced the oil flux.
Moreover, membrane equipped with only PFO shows the lowest oil
flux; however, the water permeability would be low without the alumina
nanoparticles. Alumina was added to improve the permeation of water
by assisting the water to reach the substrate. Hence, without alumina,
the membrane would rely on the PFO to transport the water to the
membrane. The flip flop mechanism indicated in this study can be
represented as follows; the polymeric coating material contains two
segments of which hydrophilic segment (head) has the hydroxyl group
while the oleophobic segment (tail) has the fluorinated group. The
fluorinated group was exposed to feed concentration, enabling the oil
repellence as its drops on the coated surface. Its hydroxyl group is
attached to the solid substrate (stark membrane), which allows water
molecules to penetrate.
Hence, this liquid penetration mechanism guarantees high oil con­
tact angle when oil is in contact with the coated top layer and a low
water contact angle when the water molecule drops onto the surface
[27]. Therefore, based on the flip-flop mechanism, the chemical struc­
ture in Fig. 2 would react freely in a flip-flop pattern when approached
with either water or oil molecules. For oil flux, the oleophobic group
would detest the oil but at the same time allowing the water to pass
through with its hydrophilic tails. Although the water and oil have been
emulsified, the possibility of PFO-Alumina to separate the emulsified
solution can still occur which explains the reduction in oil flux in a
membrane equipped with PFO.
Meanwhile, once the water has been separated from the oil-water
emulsion, due to the slow water transporting mechanism towards the
substrate, the water attached at the hydrophilic group (alumina) would
create a film repelling the oil. It is postulated that water attached to the
hydrophilic group would detach from the emulsifier, thus developing a
repellent characteristic usually associated with water when mixed with
oil. This film of water is the second mechanism that explains the
reduction in oil flux, especially for membrane equipped with alumina.
Furthermore, unlike PFO only membrane, the formation of water film on
Y.O. Raji et al. Ceramics International 47 (2021) 25883–25894

top of the membrane has improved the water permeation, which was the
primary objective of utilizing an oleophobic membrane in the first place.
Fig. 10 depicts the inclusion of alumina that promotes water film for­
mation that increases the water permeation and restricts oil, while the
PFO-only membrane affects the passage of water with its excellent oil-
repellent properties.

3.6.2. Pure water flux test

Fig. 11 displays the pure water flux performance for stark membrane
and stark membrane coated with PDADMAC-PFO and PDADMAC-
Al2O3/PFO. As expected, the PFO membrane without alumina suffers
from poor water flux due to a lack of alumina hydrophilic group, while
the membrane with alumina excels in water flux. The observation is in
agreement with the previous claim that the formation of water film on
top of the membrane surface would improve the water permeation. The
final flux for alumina/PFO membrane was ~27 L/m2. h, while PFO
equipped membrane only reported ~3 L/m2. h. The large gap between
the membrane revealed that PDADMAC-Al2O3/PFO membrane pos­
sesses a balance performance with regards to oil and water flux.
3.6.3. Antifouling test
The stark membrane coated with 44 wt% PFO showed more fouling
resistance than those coated with 22 wt% PFO, PFO and stark membrane
as shown in Fig. 12. For instance, when using 3 g/L oil concentration,
the stark membrane, PFO-coated stark membrane, 22 wt% PFO-coated
stark membrane, and 44 wt% PFO-stark membrane exhibited fouling
resistance values of 42.3, 48.0, 54.1 and 60.4% respectively. Therefore,
it is more desirable to use stark membrane coated with 44 wt% PFO for
emulsified oil-water as the high fluorination that aggregates on the
membrane surface can decrease the membrane fouling, causing less oil
pore blockage [41]. Furthermore, fouling resistance of stark membrane
with MF will be lower due to the large pore size compared to the other
PDAMAC-Al2O3/PFO-coated membranes. This could be possibly due to
the feedstock passage filled with small flocs of emulsified oil through the
coated membranes which result from cake formation at the membrane
surface, causing less pore plugging fouling [41,42].
3.6.4. Oil rejection test
The performance of coating cycles and feed pressure on oil rejection
was also evaluated. Oil rejection suggests an increase from 90 to 99%
(Fig. 13a). This can be attributed to the presence of the PDADMAC-PFO/
Al2O3 on the stark membrane, which caused oil to be repelled (as
Fig. 11. Pure water flux for different membranes.
observed via OCA), hence providing higher rejection [43]. The effect of
pressure on the oil rejection reveals a decline with respect to feed con­
centration from 1 to 3 g/L (Fig. 13b).
Based on the trends for different initial concentration, the reduction
in rejection was expected due to the increase in oil molecule, but the PFO
loadings remain similar, limiting the amount of oil that PFO could repel.
In this case, two factors contribute to the reduction in oil rejection at
different initial oil concentrations; limited PFO and alumina inclusion. It
is inferred that 1000 ppm PFO was created for simplification when a
successful coating materialized on the membrane surface. Hence, if one
PFO can repel one oil molecule, therefore, for 1 g/L or 1000 ppm of oil-
water emulsion, the membrane could completely separate all the oil
from the water. However, in Fig. 13b, at 1 bar pressure, the oil rejection
was ~99% showing a discrepancy between the estimated and experi­
mented values. Based on this difference, it was postulated that at 44 wt%
PFO, the membrane has an efficiency of 99% for removing 1 g/L oil-
water emulsion.
Meanwhile, at a higher initial oil concentration, the performance
was reduced to ~86%, hence confirming the earlier argument that the
lower capacity of PFO exhibits a significant efficiency for oil repellent.
To maintain the 99% oil rejection performance, the loading of PFO must

Fig. 10. Oil-water repellent diagram according to flip-flop mechanism that induces water film formation on the membrane surface.

25891
Y.O. Raji et al.
Fig. 12. Fouling resistance (%) of the stark membrane, stark membrane coated
with PDADMAC-PFO, stark membrane coated with PDADMAC-Al2O3/22 wt%
PFO, and stark membrane coated with PDADMAC-Al2O3/44 wt% PFO.
be increased to at least twice the current loading, which was impossible
and could overshadow the hydrophilic characteristic of alumina and
restrict water transport. In this case, it was suggested to arrange the
membrane in series if the required permeate must contain less than 1%
oil. Fig. 14 illustrates the effect of different initial oil concentrations on
the membrane with similar PFO loadings, which indicates that an in­
crease in oil droplets has saturated the PFO, thus reducing its efficiency
in repelling the oil.
Another factor that contributes to reducing oil rejection was the in­
clusion of alumina. Alumina is the hydrophilic group that assists the
transport of water in coating to the substrate. Besides assisting water
transport, another role of alumina was to increase membrane surface
roughness. In general, a rougher surface would refrain oil from attaching
the membrane surface, which would improve the oil rejection and
promote higher water flux. Therefore, to improve oil rejection, another
approach is to increase the surface roughness by increasing the alumina
loadings. As depicted in the Supplementary information (Fig. S1), the
incorporation of alumina on the substrate, increases the overall surface
roughness of the membrane, supporting the earlier claim that alumina
contributes to membrane surface modification.
Furthermore, at a pressure of 1 bar, the rejection decreased from 98
to 84% and a similar trend was observed at 2 and 3 bar. This decrease
Fig. 13. Oil rejection relative to (a) number of coating cycles, (b) pressure at different concentrations (1 g/L, 2 g/L and 3 g/L; sample of sample, n = 3).
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Ceramics International 47 (2021) 25883–25894
can be ascribed to an increase in the feed concentration at a lower
pressure compared to higher pressure of 2 and 3 bar. At a pressure of 3
bar, the rejection was highest, but a decline in the oil rejection from 99
to 96% was also observed when the feed concentration was increased.
The fouling resistance was decreased due to the collection of oil droplets
(cake fouling) on contacting the membrane surface. The increase in oil
rejection at higher pressure, as illustrated in Fig. 13 (b) was due to cake
fouling and pore blockage. At 3 bar, the rate of feed reaching the
membrane surface was threefold higher than at minimum pressure of 1
bar. The increase in pressure would force more feed to permeate through
the membrane. The sudden increase in pressure in combination with
high initial concentration has formed a cake layer on top of the mem­
brane. In protein filtration test, the formation of cake layer would reduce
the membrane flux but improve the protein rejection. Therefore, it can
be inferred that the layer of cake made of oil would act similar to pro­
tein. Based on the condition, it is assumed that higher pressure with
higher initial oil concentration would create the cake layer faster than its
counterpart which explains the improvement in the oil rejection for
membrane filtering higher oil concentration (see Supplementary infor­
mation, Fig. S2).
Another reason for the increase in oil rejection at higher pressure was
the possibility of pore blockage. At higher pressure, the oil molecule is
forced to pass through the coating of PFO, and when it reaches the
substrate, there is a high possibility that the bigger oil molecule will clog
the membrane pore. Besides the cake layer, the pore blocking would
directly contribute to higher oil rejection and simultaneously reduce the
water flux. Although, high oil rejection is desired outcome in membrane
filtration, a balance between water permeation and oil rejection is vital
to produce a membrane that is suitable for oil-water separation.
4. Conclusions
Superhydrophilic and superoleophobic surfaces were fabricated
using a simple dip-coating of the stark membrane with synthesized
PDADMAC-Al2O3/PFO nanocomposites. Water droplets were able to
penetrate through the coated surface due to the water-molecule induced
rearrangement, and the microstructure caused the hierarchical capillary
effect. The membrane coated with PDADMAC-Al2O3/44 wt% PFO
showed excellent wettability properties and separation performance at
coating cycle and chemical stability. OCA increased with an increase in
the 5-coating cycle, while WCA decreased with an increase in the
coating cycle. This suggested that PFO and nanoparticles played a sig­
nificant role in affecting the wettability properties of the membrane. The
coated membrane maintained good chemical stability at pH3
throughout 7 days of the test. Oil showed a high contact angle of 155◦ ,
Y.O. Raji et al.
Fig. 14. Schematic representation of the effects of different oil concentration on PFO in repelling oil. At higher oil concentration, the limited amount of PFO proves
to be insufficient in preventing oil from permeating the membrane.
and the material also displayed outstanding water permeation and
strong oil-repelling behaviour, leading to oil-water separation with high
separation capacity and simple recyclability. The oil flux and oil rejec­
tion results of the membrane were obtained at 63.0 L/m2. h and 98%,
respectively. Hence, high concentration of fluorinated group from the
PFO resulted in its extreme wettability surface. Therefore, the PDAD­
MAC-Al2O3/PFO, complex-polymer nanocomposite used as a coating on
a substrate can be a good entrant for the treatment of industrial oil-water
pollution and the cleaning up of oil spills.
Declaration of competing 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
Acknowledgements
This study was funded by the Ministry Higher of Education Malaysia
under the Malaysia Research University Network (MRUN) Grant (Proj­
ect no. RJ130000.7809.4L867) and Higher Institution Centre of Excel­
lence Scheme (Project no. R.J090301.7809.4J430) and Universiti
Teknologi Malaysia under the Transdisciplinary Research University
(TDR) (Project no. Q.J130000.3509.05G75) and Industry and Interna­
tional Incentive Grant (Project no. QJ130000.3009.02M25). The au­
thors gratefully thank the Research Management Centre, Universiti
Teknologi Malaysia for the technical support. The authors also
acknowledge the financial support from the Tertiary Education Trust
Fund (TETFund), Nigeria.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.ceramint.2021.05.319.
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