Separation and Purification Technology 211 (2019) 578–586

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Separation and Purification Technology

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

Congo red dye removal by direct membrane distillation using PVDF/PTFE T

membrane
N.P. Khumaloa, L.N. Nthunyaa,b, E. De Canckb, S. Dereseb, A.R. Verliefdeb, A.T. Kuvaregaa,
⁎ ⁎
B.B. Mambaa, S.D. Mhlangaa, , D.S. Dlaminia,c,d,
a
Nanotechnology and Water Sustainability (NanoWS) Research Unit, College of Science, Engineering and Technology, University of South Africa, Florida, 1709
Johannesburg, South Africa
b
Particle and Interfacial Technology Group, Department of Applied Analytical and Physical Chemistry, Ghent University, Coupure Links 653, 9000 Ghent, Belgium
c
State Key Laboratory of Separation Membranes and Membrane Processes/National Center for International Joint Research on Membrane Science and Technology, Tianjin
300387, PR China
d
School of Materials Science and Engineering, Tianjin Polytechnic University, Tianjin 300387, PR China

A R T I C LE I N FO A B S T R A C T

Keywords:
Congo red dye
Methyl functionalized silica nanoparticles
PVDF/PTFE nanocomposite membranes
Direct contact membrane distillation
The ability to use the membrane distillation (MD) technique is envisaged as a promising approach to attain
sustainable and reliable clean water supply. In this work, polytetrafluoroethylene/polyvinylidene fluoride
(PVDF/PTFE) flat sheet membranes were fabricated via the thermally induced solvent evaporation process. The
PVDF/PTFE membrane surface was modified by incorporating methyl functionalized mesoporous silica nano-
particles (MfSNPs). Prior to application, the membranes were characterized with respect to surface and struc-
tural morphology, hydrophobicity and overall porosity. Clean water flux measurements were conducted using a
direct contact membrane distillation (DCMD) lab-scale experimental setup with deionized water as the feed
solution (50 °C) and permeate solution (20 °C). The highest stable pure water flux for the MfSNPS/PVDF/PTFE
membranes was 0.0041 L/h m2. The incorporation of the MfNPS did not only improve the fluxes but also induced
low wetting properties as shown by the contact angle and LEPw values. The MfSNPs/PVDF/PTFE membranes
were highly efficient in removing Congo red dye from water with 99% removal efficiency achieved.

1. Introduction hydrophobic membranes in MD processes [5,11,12]. However, other

Membrane distillation (MD) technology has emerged as one of the
potential membrane separation processes for production of potable
water from saline water. This technique can also be integrated in water/
wastewater treatment processes for recovery of nutrients and metals
[3–5], removal of dyes [4,5], and effluent treatment for the production
of clean water in industrial processes [1,6]. MD is a non-isothermal
membrane-based separation process [8]. This technique is based on the
diffusive and convective transportation of vapour across a hydrophobic
membrane [9]. The hydrophobic membrane serves as a barrier between
two non-isothermal solutions. The driving force across the membrane is
the partial vapour pressure gradient resulting from the temperature
difference between the bulk feed and permeate solutions [1,6,7,9].
Previous research on MD has established that polytetra-
fluoroethylene (PTFE), polyvinylidene fluoride (PVDF) and poly-
propylene (PP) are ideal polymeric materials for this application [8].
Some studies have reported the application of commercially available
studies implement post-surface modification on these commercially
available membranes to improve their performance [13,14]. In recent
studies ceramic membranes have been used in MD [14–16]. Results
from these studies have shown that the application of ceramic mem-
branes in MD may result in higher separation performance due to their
appealing properties such as: high mechanical stability, chemical and
thermal resistance and the ability to control pore geometry. However,
ceramic membranes tend to be hydrophilic due to the existence of hy-
droxyl groups on membrane surfaces, therefore surface modification is
required to make them hydrophobic, thus increasing fabrication costs
[17]. As such, polymeric membranes have remained popular for ap-
plication in MD processes.
In recent years, there has been a growing interest to fabricate
membranes with improved properties for MD applications. Current
research is focused on fabricating MD membranes with high thermal
efficiency to prevent conductive heat loss across the membrane surface
[8,18,19]. The low heat conductivity of polymeric membranes

⁎
Corresponding authors at: School of Materials Science and Engineering, Tianjin Polytechnic University, Tianjin 300387, PR China (D.S. Dlamini).
E-mail address: derricksdlamini@gmail.com (D.S. Dlamini).

https://doi.org/10.1016/j.seppur.2018.10.039
Received 28 November 2017; Received in revised form 6 September 2018; Accepted 17 October 2018
Available online 17 October 2018
1383-5866/ © 2018 Elsevier B.V. All rights reserved.
N.P. Khumalo et al.
compromises the mass transfer across the membrane resulting in low
fluxes [8]. The hydrophobic MD membrane serve as a barrier main-
taining a liquid/vapour interface formed across the membrane [16].
The liquid/vapour interface maintenance is a function of both physical
and chemical properties of these popularized polymeric membranes.
The most crucial characteristics for determining membrane applic-
ability and efficiency in MD processes are hydrophobicity, surface
roughness, thickness, porosity and pore geometry [6]. Membrane por-
osity and thickness control the mass transport of water vapor across the
membrane [20]. Enhanced membrane hydrophobicity and controlled
pore shape and size formation results in membranes with low vapour
resistance therefore achieving a high long-term permeate flux [21]. The
hydrophobic nature of the membrane prevents penetration of the
aqueous solution into the pores, while pore sizes and shapes determine
the diffusion or convection across the membrane. However, membrane
flux is also affected by operational conditions such as heat gradient
across membrane and direct contact membrane distillation (DCMD)
module design (surface area) [21]. Hydrophobicity and pore geometry
influence the magnitude of liquid pressure entry.
Recently, functionalizing mesoporous silica nanoparticles with me-
thyl groups has gained interest for use in MD membranes. This is mainly
because the organic functional groups replace the hydrophilic methyl
groups thus resulting in more ‘super-hydrophobic’ silica nanoparticles
[22,23]. In this study the main objectives were: (1) to evaluate the
effect of methyl functionalized silica nanoparticles (MfSNPs) on the
structural morphologies of the fabricated MfSNPs/PVDF/PTFE flat
sheet membranes and (2) to evaluate the performance of the fabricated
membranes in Congo Red (CR) dye removal using the DCMD config-
uration. The membranes were fabricated via thermally induced solvent
evaporation and the membrane surface was modified by incorporating
MfSNPS.
2. Experimental
2.1. Materials
Poly(ethylene glycol) and polypropylene glycol (P123), tetraethyl
orthosilicate (TEOS), hydrochloric acid (HCl), hexamethyldi-silazane
(HMDS), powdered poly(vinylidene) fluoride (PVDF), powdered poly
(tetrafluoroethylene) (PTFE), N-methyl-2-pyrrolidone (NMP) and
acetone were purchased from Sigma Aldrich and were used as-received.
The materials were used in different experiments discussed in Sections
2.3-2.5.
2.2. Synthesis of silica nanoparticles (SNPs)
Mesoporous silica nanoparticles (SNPs) were synthesized following
a modified procedure first reported by Zhao and co-workers, (1998)
[24] (Fig. 1). An amount of 4 g of P123 (structure directing agent) was
dissolved in 120 mL of 2 M HCl and 30 mL of distilled water (DI water).
The mixture was vigorously stirred at ambient conditions until the
surfactant was completely dissolved. TEOS (9.1 mL) was added into the
mixture and the temperature increased to 45 °C for 5 h under stirring. A
white precipitate was formed. Subsequently, the temperature was
raised to 90 °C for 18 h at static conditions. The mixture was allowed to
cool to room temperature and the solids were filtered and washed 3
times with deionized water and acetone. Finally the nanoparticles were
calcined at 550 °C for 6 h. The nanoparticles were characterized by
nitrogen sorption measurements to determine their surface area, pore
size and pore volume.
2.3. Functionalization of the SNPs nanoparticles
Mesoporous silica (0.9 g) was dispersed in hexamethyldisilazane
(HDMS) and the mixture was vigorously stirred for 5 h at 30 °C to
functionalize the SNPs with hydrophobic methyl groups (Fig. 2). After
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Separation and Purification Technology 211 (2019) 578–586
functionalization, the mixture was filtered and washed several times
with pentane. The resultant material denoted as MfSNPs, was dispersed
in pentane and the mixture was vigorously stirred for 1 h at 30 °C to
wash-off all the unreacted HMDS from the nanoparticles. The methyl
functionalized silica nanoparticles (MfSNPs) were filtered and vacuum
dried at 120 °C. Infrared spectroscopic measurements and nitrogen
sorption were performed to confirm the successful functionalizing
through functional (methyl) group identification.
2.4. Membrane fabrication
The membranes were fabricated following a modified method re-
ported by Dong et al., 2014 [25]. Powdered PVDF was dissolved in N-
methyl-2-pyrrolidone (NMP) under vigorous magnetic stirring, then
different PTFE concentrations (0, 3, 6 wt%) were added into the dis-
solved PVDF solution to obtain the viscosity that allows casting. The
mixture was vigorously stirred for 48 h, at 50 °C. The casting solution
was degassed and cast using a casting knife, controlling the thickness of
the membranes to 0.20 mm for membranes without nanoparticles. For
the synthesis of nanocomposite membranes a double casting method
reported by Mahlangu et al., 2017 was used [26]. In this method, so-
lution A (solution without the nanoparticles) was cast using a casting
knife with the gap clearance of 0.18 mm then a second solution (solu-
tion B, containing nanoparticles (0.3 and 0.5 wt%)) was cast on top of
the first layer using a casting knife with the gap clearance 0.02 mm. The
casting knife was quickly cleaned, and the double casting was done in a
period of 30 s to avoid the coagulation of the pre-cast polymer solution
from air-moisture. The cast solutions were exposed to air and immer-
sion precipitation (IP) phase inversion method was used to produce thin
film membranes. The membranes were dried between filter papers and
annealed at 60 °C for 1 h. The composition of the nanocomposite
membranes is presented in Table 1. The membranes were prepared 3
times and the procedure was found to be reproducible.
2.5. Characterization of the nanoparticles and membranes
The chemical composition and porosity of the nanoparticles are
important parameters that can be used to confirm the functionalization
of the mesoporous silica nanoparticles. Diffuse Reflectance Infrared
Fourier Transform Spectroscopy (DRIFTS) was performed using a
ThermoNicolett 6700 FT-IR spectrometer with a custom-made DRIFT
cell at 120 °C under vacuum. Nitrogen sorption experiments were exe-
cuted on a Micromeretics Tristar at 77 K to obtain the internal surface
area via the Brunauer-Emmett-Teller (BET) theory (SBET) and pore size
distribution (dp,BJH) using the Barrett-Joyner-Halenda theory. The pore
volume (Vp) was determined at P/P0 = 0.95. AXIS SupraTM is an X-ray
photoelectron spectrometer (XPS) with unrivalled automation and ease
of use was used for materials surface characterization. The nano-
particles were prepared into a pellet form with the size of 1–1.5 mm
diameter. The prepared membranes were subjected to Fourier trans-
form infrared-attenuated total reflection (FTIR-ATR) spectroscopic
measurements (Perkin Elmer FTIR spectrometer (Frontier Optica)) to
obtain a good representation of the surface functional groups on the
membrane surface. Water contact angle analysis were measured to as-
sess the hydrophobic/hydrophilic properties of the membranes using a
DSA3OE Kruss Drop shape analyzer, (GmbH, Germany).
2.6. Membrane testing experimental design
For the preparation of the feed solution, a stock solution (1000 mg/
L) was prepared by weighing 1 g of CR dye and dissolving in 1 L
deionized (DI) water under vigorous stirring for 3–4 h. The experi-
mental feed solutions were prepared by diluting the dye stock solutions
to 100 mg/L in a 2 L volumetric flask. Flux and rejection measurements
were conducted using a DCMD lab-scale experimental setup with
deionized water. The feed temperature was kept at 50 °C while the
N.P. Khumalo et al. Separation and Purification Technology 211 (2019) 578–586

Fig. 1. Synthesis procedure of the silica (SiO2) nanoparticles.

Fig. 2. Functionalization of the SiO2 network.

Table 1
Casting solution composition of the fabricated membranes.
Membrane type PVDF (wt%) PTFE (wt%) MfSNPs (wt%)

M-1 15 0 0.3
M-2 15 3 0.3
M-3 15 6 0.3
M-4 15 0 0.5
M-5 15 3 0.5
M-6 15 6 0.5

Fig. 4. FTIR Spectra of the synthesized membranes. The compositions of M-1 to

M-6 are presented in Table 1.

Table 2
Specific surface area, pore volume and pore dimeter for SNPs and MfSNPs.
Property SNPS MfSNPs

2
Specific surface area (SBET) 667 m /g 361 m2/g
Pore volume (VP) 0.69 mL/g 0.49 mL/g
Pore diameter (DP) 9.1 nm 5.2 nm

(corresponding to a cross flow velocity of 0.4 m/s). The rejection per-

Fig. 3. DRIFTS spectra for the synthesized nanoparticles.
permeate was kept at 20 °C to create a temperature gradient. The pre-
pared membranes were inserted in the cross-flow mode module with a
membrane surface area of 0.0125 m2. The feed solution and permeate
solutions were circulated at an operational speed of 35 L/h average
formance of the membranes was evaluated using CR dye, where the
filtrate samples were collected after reaching a steady flux rate and the
feed solution was vigorously stirred to maintain homogenous mixture of
the feed solution. The rejection rate was estimated by the difference in
the concentration of the feed and permeate. CR dye measurements were
performed using UV–vis spectroscopy.
The removal efficiencies of the membranes were calculated using
the Eq. (1):

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Fig. 5. Nitrogen sorption-desorption isotherms (left) and pore size distribution (right) of the synthesized nanoparticles: SNPS (a and b) and MfSNPS (c and d).

Table 3 3. Results and discussion

Elemental quantification for SBA-15 NPs.
Quantification
3.1. DRIFTS and FTIR analysis

Atomic conc. [%] Error [%] Mass conc. [%] Error [%] Fig. 3 shows the DRIFTS spectra of the silica nanoparticles (SNPs)
and methyl functionalized silica nanoparticles (MfSNPs). The broad
SNPs O 1s 69.16 0.32 56.09 0.37
Si 2p 30.84 0.32 43.91 0.37
band at 3746 cm−1 and the intense peak at 1253 cm−1 on the SNPs
spectra are attributed to hydrogen bonding in molecular H2O. The
MfSNPs C 1s 20.25 0.51 14.28 0.37
broad band between 3500 and 3300 cm−1 originated from internal and
O 1s 58.34 0.42 52.06 0.34
Si 2p 21.41 0.26 33.67 0.32 water related H-bonding. The band at 740 cm−1 corresponds to Si-O2
stretching and deformation vibrations. The silanol peak disappeared
completely in the MfSNPs spectra due to the reaction with the trimethyl
Cf −Cpt ⎞ silyl function. Additionally, some new signals appeared at 1226 cm−1
%Removal = ⎛ ⎜ × 100
⎟

⎝ Cf ⎠
where Cf and Cp are the feed and permeate concentrations, respectively.
The flux was calculated using Eq. (2):
Jwater = (Mt + 1−−Mt )/(tt + 1−−tt )Am
where the membrane surface is denoted as Am, Mt+1 and Mt are the
permeate masses at time tt+1 and tt, respectively.
(1) originating from the newly introduced methyl groups. These observa-
tions clearly confirmed the successful introduction of methyl functions
on the SNP materials.
Different FTIR absorption bands of the polymers correspond to
different PVDF polymorphs. For example, the signals at 763 cm−1 and
(2) 840 cm−1 correspond to α and β forms of PVDF [28,29]. In Fig. 4, the
signal at 763 cm−1 corresponds to the in-plane bending or vibration of
the α-phase, whereas the band at 840 cm−1corresponds to the

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Fig. 6. (a) XPS survey scan for the SNPs and MfSNPs capped nanoparticles, and (b), deconvoluted C 1s spectrum of the methyl functionalized silica nanoparticles.
Fig. 7. Measured contact angles for nanocomposite membranes.
vibrations of the CH2 groups and the asymmetric stretching of the β
phase. The band at 1153 cm−1 corresponds to the CF2 group symme-
trical stretching whereas 1482 cm−1 corresponds to γ phase. The most
interesting band is the wide band at 1263 cm−1 which may be attrib-
uted Si-C stretching and deformation vibrations therefore suggesting
the presence of MfSPNs on the surface of the membranes. The trans-
mittance of the α-band at 763 cm−1has noticeably decreased indicating
chemical changes on the polymorph of the PDVF brought about by
inclusion of the nanoparticles.
3.2. Brunauer-Emmett-Teller (BET) analysis
The BET nitrogen sorption measurements determine the mean sur-
face area, pore volume and pore diameter of the nanoparticles. The
effect of functionalizing using HMDS on the pore size and surface area is
presented in Table 2. After functionalization of the SNPs, a significant
decrease in the surface area, pore volume and pore diameter was ob-
served. This was attributed to trimethyl-silyl functions decorating the
pores. Therefore, confirming that the nanoparticles fabricated had a
porous structure.
Fig. 5(a) and (c) depict a typical 77 K N2sorption isotherm for the
SNPs and MfSNPs, respectively. The sorption isotherms have both
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Separation and Purification Technology 211 (2019) 578–586
nitrogen adsorption (lower curve) and desorption (upper curve) of the
isotherm measured. The lag-loop (hysterisis) observed between the
adsorption and desorption isotherms indicates the existance of meso-
porous pores on both the SNPs and MfSNPs. The pore distribution of the
SNPs and MfSNPs (Fig. 5(b) and (c), respectively) indicate that the
nanoparticles were smaller in size with a small pore size distributoin of
3–10 for MfSNPs and 7–12 SNPs indicating a decrease in the pore size.
3.3. X-ray photoelectron spectroscopy analysis
Surface elemental compositions of the nanoparticles are presented
in Table 3. The XPS results suggest that the atomic concentration of
carbon on the MfSNPs was 20.5% indicating that the signal was not due
to the adsorption of carbon dioxide (CO2) on the surface of the nano-
particles but attributed to the methyl groups. It was observed that the
atomic concentration of oxygen on the MfSNPs was lower than that of
the SNPs.
Fig. 6(a and b) shows the XPS spectra of the raw SNPs and the
MfSNPs. The peaks at 103.5 eV (Si-O) and 150.5 eV (Si 2p) were at-
tributed to silica and the peak at 532.5 eV was attributed to oxygen (O
1s). The signal at 285.4 eV (C-OR clearly indicates that silica nano-
particles were modified (Fig. 6b). This signal was attributed to carbon
in the form of methyl group (–CH3) which confirms the functionaliza-
tion of the mesoporous silica nanoparticles by HMDS. The deconvoluted
spectra (Fig. 6(b)), shows the presence of the CeC, CeH and C 1s
bonding on the surface of the silica nanoparticles. This indicates the
bonding states of the carbon to the silica core. Metal oxides carbonates
may have hydrocarbon or carbonate on their core [27].
3.4. Contact angle measurements
The interaction of water with the surface of the membrane produces
surface tension on the membrane surface. Therefore contact angle
measurement is an important membrane characterization technique
because it the wettability of a membrane [30]. Wettability is an im-
portant factor in membrane distillation as it gives an idea of the hy-
drophobicity of the membranes. The results of the water contact angle
measurements of the nanocomposite membranes are shown in Fig. 7.
When the hydrophobic nanoparticles (nanofiller) were incorporated,
the contact angles were increased. Increasing the concentration of the
nanofiller further increased the contact angles of the nanocomposite
membranes. Small water contact angles (< 90°) correspond to high
N.P. Khumalo et al. Separation and Purification Technology 211 (2019) 578–586

Fig. 8. SEM images of the membranes (a) PVDF, (b) M-2, (c) M-4 and (d) M-6.

Fig. 9. AFM micrographs of (a) PVDF, (b) M-2, and (c) M-5.

wettability, while large water contact angles (> 90°) correspond to low
wettability [30]. As it can be observed in Fig. 7, the water contact
angles of the nanocomposite membranes were greater than 90 °C, sug-
gesting that the membranes were hydrophobic, and were thus expected
to exhibit low wettability.
3.5. Scanning electron microscopy analysis
The surface morphology and chemical composition of the MD
membranes are the two factors determining the membrane wettability
during MD application. Scanning electron microscopy (SEM) and
atomic force microscopy (AFM) are two techniques that elaborate on

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N.P. Khumalo et al.
Fig. 10. Pure water flux of the membranes in a DCMD set-up.
the surface morphology of the membranes. To investigate the surface
morphologies of the membranes; a typical JSM IT 300LV, JEOL scan-
ning electron microscopy (SEM) was used to take the micrographs after
carbon coating (Fig. 8).
It was observed from the SEM images that incorporating MfSNPS
modified the neat structure of the pristine PVDF and impacted mor-
phology changes on the pore geometry of the membrane. From the top
surface of the membranes, it can be observed that the nanocomposite
membranes possessed larger pores but fewer in number as compared to
the PVDF membranes. Membrane pores are formed by the demixing
(solvent evaporation) during the phase inversion process [31]. Since the
MSNs are hydrophobic due to methyl groups present on the surface of
the nanoparticles, their dispersal was improved in the polymeric solu-
tions as shown by the occurrence of the enlarged pores.
3.6. Atomic force microscopy analysis
In addition to SEM micrographs, atomic force microgaphs were
obtained from atomic force microscopy (AFM), WITec Alpha 300
atomic force microscope (WITec, GmbH, Germany) to investigate the
changes in the membrane surface due to the incorporation of fMSNs.
Surface roughness parameters were calculated by Control Four soft-
ware, (WITec, GmbH, Germany). The average square roughness (SA)
defines the arimethicaverage of the measured peak heights from a one
dimensional plane whereas the root mean square roughness (Sq) refers
to the standard deviation. The topography micrographs and surface
rougness parameters are presented in Fig. 9.
It was observed that the surface roughness of the PVDF/PTFE
blended membranes was larger than the pristine PVDF membranes. The
trend of these results corresponds with the surface roughness results of
commercial PVDF/PTFE flat sheet membranes (Mingle, China) [32].
The pristine PVDF membrane had the smoothest surface with
SA = 73.947 nm. There was no significant variation of roughness
Fig. 11. Removal of CR dye, (a) removal efficiency and (b) flux during the DCMD experiment.
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Separation and Purification Technology 211 (2019) 578–586
relative to PTFE concentration in the blended membranes i.e., the ad-
dition of 3 and 6 wt% PTFE did not affect the surface roughness, hence
images are not shown. It was the incoporation of nanoparticles that
increased the surface roughness of the nanocomposite membranes. M-2
(0.3 wt% MfSNPs) and M-5 (0.5 wt% MfSNPs) in Fig. 9 shows the dif-
ference. Although surface roughness is an undesirable property as it
increases membrane fouling, it is correlated to membrane hydro-
phobicity due to air entrapement in the micro voids of the rougher
membrane [6,9]. Indeed, the membranes with higher amounts of silica
nanoparticles, exhibited higher contact angles (Fig. 7). Hydrophobicity
is a key requirement in MD membranes to avoid membrane wetting
[6,9].
3.7. Flux and rejection studies
The incorporation of nanoparticles such as Al2O3, TiO2, ZrO2, SiO2
and zinc oxide (ZnO) does not only improve the mechanical strength of
PVDF membranes [33], but also membrane porosity, which positively
impacts on the membrane permeate fluxes. In this study, MfSNPs were
incorporated in the PVDF/PTFE blends and their effect on membrane
flux and rejection capacity was studied. Fig. 10 shows the effect of the
concentration of MfSNPs on membrane flux in a DCMD set-up. Com-
pared with the fluxes obtained from ‘virgin’ PVDF/PTFE membranes, it
was observed that the MfSNPs enhanced the pure water (deionized
water) flux of the nanocomposite membranes. The highest stable flux
obtained from the surface modified membrane was approximately
0.0041 L/h m2 on M-3, which was comparable to other studies [34].
The most important property of MD membranes is to maintain stable
flux as this corresponds to low wetting properties. Additionally, the
water flux was generally lower in M-5 and M-6 due to a possible re-
duction in membrane pore sizes induced by the SNP filling of the micro-
voids of the membrane.
The CR dye removal efficiency of the MfSNPs/PVDF/PTFE mem-
branes (M-1, M-4) and (M-2, M-3, M-5 and M-6), exhibited a similar
rejection, which decreased gradually with time (Fig. 11 (a)). This was
due to the increase in the CR dye concentration which may have re-
sulted in concentration polarization. This makes the membranes prone
to fouling causing the pore blockage and contamination of the permeate
solution. The MfSNPs/PVDF/3% PTFE membranes (M-5) showed a
drastic decrease in the membrane removal efficiency after 3 h possibly
due to membrane wettability induced by fouling. The driving force for
separation in MD is vapour difference across the two interfaces of the
hydrophobic membrane [16]. Membrane wetting promotes the passage
of the solutions in the liquid state. The high porous nature of these
membranes, allowed the passage of the dye molecules, which conse-
quently reduced the removal efficiency [16,21]. The removal efficiency
obtained for CR dye was comparable to the removal efficiency obtained
for methylene blue separation using DCMD [5]. Pore wetting in MD is
another challenge that can result in declining efficiency and
N.P. Khumalo et al.
deterioration of the permeate production rate and quality when using
hydrophobic membranes. Pore wetting is a result of the feed solution
passing through the pores of the hydrophobic membrane due to high
pressure. This cannot be avoided in most cases.
Fig. 11(b) illustrates the permeate flux (J/Jo) of the nanocomposite
membranes using 100 ppm CR dye. Generally, the permeate fluxes of
the all the membranes decreased with time. This was attributed to the
increase of CR dye concentration in the feed side due to the evaporation
of water molecules on the membrane surface, through the membrane
pores to the permeate side. This resulted in a difference in bulk and
membrane surface concentration, thereby contributing to the reduction
in the partial vapour pressure and therefore, a decline in the fluxes can
be experienced with time [35]. This is known as the concentration
polarization phenomena that is under investigation in a separate on-
going study. Another factor that can result in flux decline is the
blockage of membranes pores due to fouling caused by hydrophobic
interactions between the surface of the membrane and CR dye mole-
cules. M-2 had a higher flux as compared to other membranes signaling
better performance.
4. Conclusion
The MfSNPs were successfully functionalized with methyl groups as
confirmed by IR analysis and nitrogen adsorption-desorption mea-
surements. The MfSNPs obtained were hydrophobic as seen from the
water contact angle measurements of the membranes, which increased
with increasing filler loading. A 0.5 wt% loading significantly improved
the PVDF contact angle from 97° to 120°. The results confirmed that the
incorporation of the methyl functionalized MfSNPs did not only im-
prove the fluxes but also induced low wettability properties of the
membranes. Clean water flux was observed to be stable over a long
period of time in all the MfSNPs incorporated and non-incorporated
membranes. However, the feed solution containing the CR dye resulted
to the decline in fluxes as a function of time. The flux decline induced
by the CR dye solution was associated with hydrophobic-hydrophobic
membrane and dye interactions leading to membrane fouling. Although
the acid dyes are predominantly hydrophobic, they possess the hydro-
philic anionicity which can cause membrane hydrophilicity. The in-
duction of the membrane hydrophilicity reduces the vapour pressure
gradient and allows the passage of the liquid across the membrane,
hence reduce rejection efficiency as a function of time. Therefore, fur-
ther studies are required to maintain the balance between the flux and
rejection efficiency in water systems characterized by high levels of
hydrophobic solutes.
Acknowledgements
The authors would like to acknowledge the financial support from
the University of South Africa (UNISA) and Ghent University. We are
thankful to Particle and Interfacial Technology (PAINT) Group and the
Nanotechnology and Water Sustainability (NanoWS) Research Unit for
providing research facilities.
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.seppur.2018.10.039.
References
[1] C.A. Quist-Jensen, A. Ali, S. Mondal, F. Macedonio, E. Drioli, A study of membrane
distillation and crystallization for lithium recovery from high concentrated aqueous
solutions, J. Membr. Sci. 505 (2016) 167–173, https://doi.org/10.1016/j.memsci.
2016.01.033.
[3] K.M. Udert, M. Wächter, Complete nutrient recovery from source-separated urine
by nitrification and distillation, Water Res. 46 (2012) 453–464, https://doi.org/10.
1016/j.watres.2011.11.020.
585
Separation and Purification Technology 211 (2019) 578–586
[4] K.C. Chong, S.O. Lai, H.S. Thiam, S.S. Lee, W.J. Lau, N.M. Mokhtar, Reactive blue
dye removal by membrane distillation using PVDF membrane, Ind. J. Sci. Technol.
9 (2016) 1–5, https://doi.org/10.17485/ijst/2016/v9iS1/110379.
[5] A.K. An, J. Guo, S. Jeong, E.J. Lee, S.A.A. Tabatabai, T.O. Leiknes, High flux and
antifouling properties of negatively charged membrane for dyeing wastewater
treatment by membrane distillation, Water Res. 103 (2016) 362–371, https://doi.
org/10.1016/j.watres.2016.07.060.
[6] A. Alkhudhiri, N. Darwish, N. Hilal, Membrane distillation: a comprehensive re-
view, Desalination 287 (2012) 2–18, https://doi.org/10.1016/j.desal.2011.08.027.
[7] P. Wang, T. Chung, Recent advances in membrane distillation processes: mem-
brane, development configuration design and application exploring, J. Membr. Sci.
(2015), https://doi.org/10.1016/j.memsci.2014.09.016.
[8] L.M. Camacho, L. Dumée, J. Zhang, J. de Li, M. Duke, J. Gomez, S. Gray, Advances
in membrane distillation for water desalination and purification applications, Water
(Switzerland) 5 (2013) 94–196, https://doi.org/10.3390/w5010094.
[9] M.M. Teoh, T.S. Chung, Y.S. Yeo, Dual-layer PVDF/PTFE composite hollow fibers
with a thin macrovoid-free selective layer for water production via membrane
distillation, Chem. Eng. J. 171 (2011) 684–691, https://doi.org/10.1016/j.cej.
2011.05.020.
[11] M.M.A. Shirazi, A. Kargari, M. Tabatabaei, Evaluation of commercial PTFE
membranes in desalination by direct contact membrane distillation, Chem. Eng.
Process. Process Intensif. 76 (2014) 16–25, https://doi.org/10.1016/j.cep.2013.
11.010.
[12] M. Khayet, Membranes and theoretical modeling of membrane distillation: a re-
view, Adv. Colloid Interface Sci. 164 (2011) 56–88, https://doi.org/10.1016/j.cis.
2010.09.005.
[13] B.-H. Jeong, E.M.V. Hoek, Y. Yan, A. Subramani, X. Huang, G. Hurwitz, A.K. Ghosh,
A. Jawor, Interfacial polymerization of thin film nanocomposites: a new concept for
reverse osmosis membranes, J. Membr. Sci. 294 (2007) 1–7, https://doi.org/10.
1016/j.memsci.2007.02.025.
[14] Z.D. Hendren, J. Brant, M.R. Wiesner, Surface modification of nanostructured
ceramic membranes for direct contact membrane distillation, J. Membr. Sci. 331
(2009) 1–10, https://doi.org/10.1016/j.memsci.2008.11.038.
[15] S.R. Krajewski, W. Kujawski, M. Bukowska, C. Picard, A. Larbot, Application of
fluoroalkylsilanes (FAS) grafted ceramic membranes in membrane distillation
process of NaCl solutions, J. Membr. Sci. 281 (2006) 253–259, https://doi.org/10.
1016/j.memsci.2006.03.039.
[16] S. Cerneaux, I. Struzyńska, W.M. Kujawski, M. Persin, A. Larbot, Comparison of
various membrane distillation methods for desalination using hydrophobic ceramic
membranes, J. Membr. Sci. 337 (2009) 55–60, https://doi.org/10.1016/j.memsci.
2009.03.025.
[17] Y. Zhuang, F. Yu, J. Chen, J. Ma, Batch and column adsorption of methylene blue by
graphene/alginate nanocomposite: comparison of single-network and double-net-
work hydrogels, J. Environ. Chem. Eng. 4 (2016) 147–156, https://doi.org/10.
1016/j.jece.2015.11.014.
[18] C. Cabassud, D. Wirth, membrane distillation for water desalination : how to chose
an appropriate membrane? Desalination 157 (2003) 307–314.
[19] L. Eykens, K. De Sitter, C. Dotremont, L. Pinoy, B. Van Der Bruggen, How to opti-
mize the membrane properties for membrane distillation: a review, Ind. Eng. Chem.
Res. 55 (2016) 9333–9343, https://doi.org/10.1021/acs.iecr.6b02226.
[20] M. Khayet, A. Velázquez, J.I. Mengual, Modelling mass transport through a porous
partition: effect of pore size distribution, J. Non-Equilibrium Thermodyn. 29 (2004)
279–299, https://doi.org/10.1515/JNETDY.2004.055.
[21] T. Jiricek, M. Komarek, J. Chaloupek, T. Lederer, Flux enhancement in membrane
distillation using nanofiber membranes, J. Nanomater. 2016 (2016), https://doi.
org/10.1155/2016/9327431.
[22] J.E. Efome, M. Baghbanzadeh, D. Rana, T. Matsuura, C.Q. Lan, Effects of super-
hydrophobic SiO nanoparticles on the performance of PVDF flat sheet membranes
for vacuum membrane distillation, Desalination 373 (2015) 47–57, https://doi.org/
10.1016/j.desal.2015.07.002.
[23] E. Maria Claesson, A.P. Philipse, Thiol-functionalized silica colloids, grains, and
membranes for irreversible adsorption of metal(oxide) nanoparticles, Colloid Surf.
A Physicochem. Eng. Asp. 297 (2007) 46–54, https://doi.org/10.1016/j.colsurfa.
2006.10.019.
[24] D. Zhao, J. Feng, Q. Huo, N. Melosh, G. Fredrickson, B. Chmelka, G. Stucky,
Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 ang-
strom pores, Science 279 (1998) 548–552.
[25] Z. Dong, X. Ma, Z. Xu, W. You, F. Li, Superhydrophobic PVDF – PTFE electrospun
nano fibrous membranes for desalination by vacuum membrane distillation,
Desalination 347 (2014) 175–183, https://doi.org/10.1016/j.desal.2014.05.015.
[26] O.T. Mahlangu, R. Nackaerts, J.M. Thwala, B.B. Mamba, A.R.D. Verliefde,
Hydrophilic fouling-resistant GO-ZnO/PES membranes for wastewater reclamation,
J. Membr. Sci. 524 (2017) 43–55, https://doi.org/10.1016/j.memsci.2016.11.018.
[27] S. Pourbeyram, Effective removal of heavy metals from aqueous solutions by gra-
phene oxide−zirconium phosphate (GO−Zr-P) nanocomposite, Ind. Eng. Chem.
Res. (2016), https://doi.org/10.1021/acs.iecr.6b00728.
[28] J. Liu, X. Lu, C. Wu, Effect of preparation m]methods on crystallization behavior
and tensile strength of poly(vinylidene fluoride) membranes, Membranes (Basel) 3
(2013) 389–405, https://doi.org/10.3390/membranes3040389.
[29] R. Gregorio, Determination of the α, β, and γ crystalline phases of poly(vinylidene
fluoride) films prepared at different conditions, J. Appl. Polym. Sci. 100 (2006)
3272–3279, https://doi.org/10.1002/app.23137.
[30] Y. Yuan, T.R. Lee, Contact Angle and Wetting Properties, in: G. Bracco, B. Holst,
(eds), (Eds.), Surface Science Techniques. Springer Series in Surface Sciences,
Springer, Berlin, Heidelberg, 2013, , https://doi.org/10.1007/978-3-642-34243-
1_1.
N.P. Khumalo et al.
[31] B.S. Lalia, V. Kochkodan, R. Hashaikeh, N. Hilal, A review on membrane fabrica-
tion: structure, properties and performance relationship, Desalination 326 (2013)
77–95, https://doi.org/10.1016/j.desal.2013.06.016.
[32] K. Xiao, J. Sun, Y. Mo, Z. Fang, P. Liang, X. Huang, J. Ma, B. Ma, Effect of membrane
pore morphology on microfiltration organic fouling: PTFE/PVDF blend membranes
compared with pvdf membranes, Desalination 343 (2014) 217–225, https://doi.
org/10.1016/j.desal.2013.09.026.
[33] C.Y. Lai, A. Groth, S. Gray, M. Duke, Nanocomposites for improved physical dur-
ability of porous PVDF membranes, Membranes 4 (2014) 55–78, https://doi.org/
586
Separation and Purification Technology 211 (2019) 578–586
10.3390/membranes4010055.
[34] K.T. Rashid, S. Binti, A. Rahman, Enhancement the flux of PVDF-Co-HFP hollow
fiber membranes for direct contact membrane distillation applications, Ind. J. Sci.
Technol. 11 (2016) 2189–2192, https://doi.org/10.17485/ijst/2017/v10i7/
111446.
[35] T. Jiracek, M. Komarek, J. Chaloupek, T. Lederer, Flux enhancement in membrane
distillation using nanofiber membranes, J. Nanomater. 2016 (2016), https://doi.
org/10.1155/2016/9327431.