Journal of Membrane Science 556 (2018) 107–117

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Journal of Membrane Science

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

Preparation, characterization of PPS micro-porous membranes and their T

excellent performance in vacuum membrane distillation
⁎ ⁎
Tingting Fan, Zhenhuan Li , Bowen Cheng , Jianxin Li
State Key Laboratory of Separation Membranes and Membrane Processes, School of Materials Science and Engineering, Tianjin Polytechnic University, 300160 Tianjin,
China

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

Keywords: Polyphenylene sulfide (PPS) hydrophobic micro-porous flat sheet membranes were fabricated with diphenyl
Polyphenylene sulfide membrane ketone (DPK) and benzoin (BZ) as mixed diluent via thermally induced phase separation (TIPS). It was found
Thermally induced phase separation that the mass ratio of DPK/BZ had a strong influence on the structure and property of PPS membranes. As DPK
Hydrophobicity content increased, the interaction between PPS and diluents reduced linearly and the membrane micro-struc-
Distillation performance
tures changed from honeycomb, bi-continuous to spherical particle structure via liquid-liquid (L-L) phase se-
Chemical resistance
paration process. Herein, the prepared PPS micro-porous membranes were used in vacuum membrane dis-
tillation (VMD) for the first time, and they showed the strong hydrophobicity and high salt rejection ratio.
Especially, the membrane prepared from the mixed diluent of 15 wt% DPK and 85 wt% BZ with the bi-con-
tinuous network structure and Berberis thunbergii var. atropurpurea Chenault leaf-like structure achieved the
maximum permeate flux of 22.8 L/m−2 h−1 and the highest salt rejection of 99.99%. Most importantly, the
membrane with Berberis thunbergii var. atropurpurea Chenault leaf-like leaf structure performed excellent long-
term stability in corrosive water membrane distillation (MD) experiment (3.5 wt% NaCl and 10 wt% NaOH as
feed solution). Those results show the potential application of this novel type of membrane in the treatment of
corrosive sewage.

1. Introduction
Fresh water shortage is becoming a very serious problem because of
its excessive usage and increased pollution of water sources [1]. Thus,
the treatment of emerging industrial wastewater as the potential al-
ternative and reusable sources of freshwater has attracted much more
attention [2]. However, as a promising method, membrane technology
for waste water treatment demands a membrane to have excellent
chemical and thermal stability together with strong mechanical
strength [3]. The typical membrane materials, such as polyethersulfone
(PES), polyvinylidene fluoride (PVDF), polyamide (PA) and polysulfone
(PSF), can not well meet the above requirements [4]. Thus, it's neces-
sary to develop some new membranes to be used under harsh condition.
As a means of producing fresh water, MD has be received extensive
attention due to the increasing demand for desalination [5–9]. In the
MD process, only vapor molecules can be transported through a hy-
drophobic membrane. This separation process is driven by the vapor
pressure difference existing between the feed and permeate sides
[10,11]. Despite of the extensive studies on MD process, the low per-
meability, easy membrane wetting over time and fewer membranes
with excellent chemical resistance (or being used in harsh environ-
ments) remain challenges for the commercialization of MD [12]. In
order to solve these problems, MD membranes need to be designed to
exhibit high porosity, strong hydrophobicity, good thermal stability and
excellent chemical resistance to obtain higher permeability and better
long-term stability [13].
PPS is a semi-crystalline thermoplastic with asymmetrical rigid
backbone chain consisting of para-substituted phenylene rings and
sulfur atoms. As a hydrophobic material, PPS has high thermal stability
and good mechanical properties, especially, it has excellent chemical
resistance, including anti-acid, anti-alkali, anti-chlorine, anti-polar
solvents and anti-caustic organic solutions [14]. These excellent prop-
erties make PPS to be a promising membrane material for MD in harsh
environments (strong acid/alkali and organic solution and so on).
However, it is not feasible to fabricate PPS membrane via conven-
tional methods such as non solvent induced phase separation (NIPS)
because PPS is insoluble in any solvents below 200 °C [15]. Therefore,
to fabricate PPS membranes via thermally induced phase separation
(TIPS) was a promise method. In this method, a homogeneous polymer-
diluent solution formed at a sufficiently high temperature by blending

⁎
Corresponding authors.
E-mail addresses: Zhenhuanli1975@aliyun.com (Z. Li), Bowen15@tjpu.edu.cn (B. Cheng).

https://doi.org/10.1016/j.memsci.2018.03.084
Received 28 October 2017; Received in revised form 30 March 2018; Accepted 30 March 2018
Available online 04 April 2018
0376-7388/ © 2018 Elsevier B.V. All rights reserved.
T. Fan et al.
the polymer with diluent. After that, the solution was cooled at con-
trolled rate to induce phase separation and polymer solidification, and a
porous membrane obtained after the extraction of diluent [16,17]. TIPS
technology has been used to prepare a wide range of polymeric mem-
branes [18], such as polypropylene (PP) [19,20], poly (ethylene
chlorotrifluoroethylene) (ECTFE) [17,21], polyacrylonitrile (PAN)
[22,23], poly(vinylidene fluoride) (PVDF) [24–28], poly(ethylene-co-
vinyl alcohol) (EVOH) [29,30] and polyamide 6 (PA6) [31]. However,
few studies have reported on the fabrication of PPS membranes from
PPS/diluent systems via TIPS. Ding et al. [32] used diphenyl sulfone
(DPS) or diphenyl ketone (DPK) as the single diluent to prepare PPS
membranes. Zheng et al. [33] investigated the effect of six different
single solvent on the different phase separation mechanism (L–L or
S–L). All these PPS membranes prepared by PPS/single diluent systems
achieved the monotonic structures with poor mechanical properties. In
order to get a better membrane structures, a few modified TIPS methods
were introduced, such as the non-solvent thermally induced phase se-
paration (NTIPS) method [34] and the thermally assisted evaporative
phase separation (TAEPS) [35]. However, the membrane structures
obtained with these methods were still difficult to be controlled.
Recently, the fabrication of membrane using mixed diluents via
TIPS method has attracted much more attention which showed the
good performance in controlling membrane structures. For example, Ji
et al. [25] used the diluent mixtures of dibutyl phthalate (DBP) and di
(2-ethylhexyl) phthalate (DEHP) to prepare PVDF hollow fiber mem-
branes. When the ratio of DBP/DEHP was 30/70 (w/w), the prepared
membrane presented the higher water permeability and better solute
rejection property. Liu et al. [36] used a mixture of di-(2-ethylhexyl)
phthalate (DEHP) and tributyl citrate (TBC) as the diluent to prepare
PVDF membranes. When DEHP content increased in the diluent mix-
ture, the structure of membrane changed from spherulitic structure to
bi-continuous structure. Pan et al. [37] used diethyl phthalate (DEP)
and bis(2-ethylhexyl)adipate (DOA) as the mixed diluent to prepare
poly (ethylene chlorotrifluoroethylene) (ECTFE) membranes. When the
ratio of DOA/DEP was 25/75, the membrane displayed much higher
permeability and better pollution resistance than the membrane pre-
pared from single DOA.
In this work, PPS membranes with Berberis thunbergii var. atro-
purpurea Chenault leaf-like micro-porous structure were prepared from
the diluent mixture of DPK and BZ via TIPS method. Those special
membrane structure significantly improved the hydrophobicity and
permeability of PPS membrane, and the membrane structures could be
well controlled by the diluent mixture composition. The effects of DPK
content on PPS membrane performance in permeability, hydro-
phobicity and mechanical strength were also investigated.
Subsequently, these prepared PPS hydrophobic membranes were tested
in VMD.
2. Experimental section
2.1. Materials
PPS resin, which used in this study, was supplied by Tianjin
Petrochemical Co.,Ltd., China Petroleum & Chemical Corporation
(SINOPEC). DPK (99%, Mw = 182.22, ρ = 1.11 g/cm3) was provided
by Aladdin. BZ (99%, Mw=212.24, ρ = 1.31 g/cm3) was purchased
from Tianjin Guangfu Chemical Research Institute. The boiling points of
DPK (b.p. 305.4 °C) and BZ (b.p. 334 °C) were much higher than the
melting point of PPS (278 °C). The Hansen solubility parameters of DPK,
BZ and PPS were 22.1, 21.2, 25.6 MPa1/2 [38,39], respectively. All the
chemicals were used without further purification.
2.2. Phase diagram
The cloud point temperature (Tcloud) and crystallization tempera-
ture (Tc) of PPS/DBK/BZ ternary systems were measured by methods
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Journal of Membrane Science 556 (2018) 107–117
Fig. 1. Schematic diagram of PPS membrane preparation device.
described in previous literature [40]. PPS and diluents were mixed in a
glass flask at an elevated temperature (265 °C) for 15 min under ni-
trogen atmosphere. Then, the solution was quenched into a liquid ni-
trogen bath to solidify the sample. The obtained solid sample was cut
into small pieces and placed between a pair of microscope cover slips.
The sample was heated on a hot stage (THMS-600, Linkam, UK) to
280 °C (10 °C min−1) and held for 2 min, and then cooled to 100 °C
(5 °C min−1). Tcloud was visually determined by noting the appearance
of turbidity under a BX51 optical microscope (Olympus, Japan). Tc was
determined by differential scanning calorimetry (DSC 200 F3, Netzsch,
Germany). The solid sample was melted at 280 °C for 2 min, then cooled
to 30 °C at 10 °C min−1 during the cooling process, the temperature of
the exothermic peak was considered to be Tc.
2.3. Preparation of PPS flat sheet membranes
PPS (25 wt%) and diluents in a glass flask were heated at 265 °C in
nitrogen atmosphere and were stirred for 15 min to gain homogeneous
solution. After degassing air bubbles, the homogeneous solution was
quickly poured onto the surface of stainless steel plate (Fig. 1) which
was preheated to 270 °C on top of heating plate (Shanghai Bangxi In-
struments Technology Co., China), and it was quickly scraped with a
casting bar (500 µm). After that, the casting solution attached on the
plate was immediately immersed into coagulation bath (water, 25 °C) to
solidify the sample. The wet membranes were immersed in hot ethanol
for 48 h followed by being immersed in pure water for another 48 h to
remove the diluents. The obtained membranes were freeze-dried using
a FD-1D-80 freeze-dryer. These membranes were named M-d0, M-d10,
M-d15, M-d20, M-d25 in according to the diluent mixture weight ratios
of DPK/BZ which were 0/100, 10/90, 15/85, 20/80, 25/75 wt%/wt%,
respectively.
2.4. Characterization of membrane
2.4.1. Morphologies observation
Field emission scanning electron microscopy (FESEM, S-4800,
Hitachi, Japan) was applied to observe the morphologies of the surface
and cross-section in PPS membrane samples. The dry PPS membranes
were immersed in liquid nitrogen bath and freeze-fractured. All samples
were coated with gold and characterized by SEM with an accelerating
voltage of 10 kV.
The surface morphology of prepared membranes was analyzed by
an atomic force microscope (AFM) (Multimode8, Bruker, Germany)
using the tapping mode. The mean surface roughness (Ra) of membrane
samples was obtained by employing software for image analysis.
2.4.2. Membrane porosity and average pore size
Membrane porosity was determined by the gravimetric method
[41], which calculated the weight of liquid contained in the membrane
pores. Firstly, the dry weight of membrane was measured, and then the
membrane sample was immersed in the 1-butanol for 24 h. Lastly the
wet weight of membrane was measured. The porosity of membrane was
determined from the following Eq. (1):
Ww − Wd
ε= × 100%
A×d×ρ (1)
where Ww is the weight of the wet membrane (g), Wd is the weight of
T. Fan et al. Journal of Membrane Science 556 (2018) 107–117

Fig. 2. Schematic diagram of the experimental VMD apparatus.

the dry membrane (g), A is the membrane area (cm2), d is the mem- Each sample was measured at least five different positions.
brane thickness (cm), and ρ is the 1-butanol density (0.81 g/cm3).
Automatic Mercury Porosimeter (IV-9500, Tektronix, USA) was
2.4.5. Liquid entrance pressure (LEP)
used to evaluate the average pore size of PPS membranes.
The LEP of dry PPS membranes was determined using a laboratory
device at room temperature, as shown in Fig. S1. The feed solution was
2.4.3. Mechanical strength
3.5 wt% NaCl. The pressure was slowly increased until the abrupt
The tensile strength and breaking elongation of PPS membranes
change of the conductivity meter, which was considered to be the LEP
were determined at ambient temperature, using an CMT4503 tensile
point described elsewhere [42]. The average value of five tests was the
tester (Meitesi Industry Co., China) at a tensile rate of 10 mm/min. The
LEP of membrane.
membrane samples were cut into 5 (width) × 25 mm (length) strips,
and the thickness of strips was measured by a thickness gauge. Every
specimen was tested by 10 times to obtain the average value. 2.5. Chemical stability of PPS membranes

2.4.4. Contact angle
The surface wettability of PPS membrane was characterized by a
contact angle meter (DSA100, KRUSS Co., Germany). A 2 mL droplet of
water was formed on the membrane surface using a syringe, then the
water contact angle (WCA) was determined by the instrument software.
In order to test the chemical resistance of PPS membrane, mem-
branes were immersed in HCl solution (pH = 1), NaOH solution
(pH = 13), NMP/DMF/DMSO organic mixed solvent (VNMP/VDMF/
VDMSO = 1: 1: 1) for 48 h. The SEM images, thicknesses and water
contact angles of those treated membranes were tested.

Fig. 3. (a) The phase diagram of PPS/DPK/BZ samples and (b) relation between DPK/BZ ratio and interaction parameter.

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Fig. 4. SEM images of cross-section of different PPS membranes (a: M-d0, b: M-d10, c: M-d15, d: M-d20, e: M-d25; 1: whole cross-sections ×400, 2: cross-section ×
10,000).

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T. Fan et al.
Table 1
Porosity, average pore size and thickness of the membrane samples.
Samples M-d0
Porosity (%) 64.7 ± 3.6
Average pore size (nm) 181.3
Thickness (μm) 214.3 ± 5
2.6. Membrane desalination experiments
The desalination performances of PPS membranes were tested with
VMD using a home-built equipment which was shown in Fig. 2. The
feed solution (3.5 wt% NaCl) was pre-heated, and then the hot salt
solution was circulated to the bottom surface side of the membrane. The
effective membrane area was 6.15 cm2 and the type of device that was
used to heat the feed solution was digital thermostat water bath (2KYY,
Yuhua Instrument Co., Ltd., Gongyi, China). A vacuum pump was
connected to the other side of the membrane, and the vacuum pressure
was adjusted to 0.08 MPa. The permeate vapor was subsequently con-
densed and collected in a glass bottle as the product. The water
permeate flux was calculated by the following Eq. (2):
V The temperature gap between Tcloud and Tc of PPS has a great in-
Ј=
A×t
where V is the volume of the permeate (L), A is the effective membrane
area (m2), t is the running time (h). The conductivity of the feed solu-
tion and the permeate water was measured by a conductivity meter
(FE30K, Toledo, China), and the concentration was calculated by the
linear relationship between conductivity and concentration, which was
described in literature [42,43]. The salt rejection R was measured by
the following Eq. (3):
σp
R = (1− ) × 100%
σf
where σf and σP are the electrical conductibility of the feed solution and
permeate water (μs/cm), respectively.
3. Results and discussion
3.1. Phase diagram
The phase diagram of PP/DPK/BZ solutions was shown in Fig. 3a.
The cloud point temperature (Tcloud) significantly decreased from 243.2
to 217.1 °C while crystallization temperature (Tc) slowly declined from
211.8 to 206.5 °C with the increase of DPK concentration. The region
between the lines of Tc and Tcloud belonged to L-L phase diagram, but
the temperature gap between Tcloud and Tc reduced gradually. The in-
teraction between PPS and binary diluents, in terms of the interaction
parameter χ, was calculated by the below equations:
Vi
χ= (δi − δj )2 + 0.34
RT
Vi = V1 ∅1 + V2 ∅2
δi = δ1 ∅1 + δ2 ∅2
where R = 8.314 was ideal gas constant, T = 298 K (25 °C), Vi was the
molar volume of diluent, Vi = Mi /ρi, δi was the solubility parameter of
diluent, δj was the solubility parameter of polymer, V1 was the molar
volume, ∅1 was the volume fraction, and δ1 was the solubility para-
meter of one diluent, meanwhile, V2, Φ2, δ2 was those of another di-
luent, respectively.
The interaction between PPS and binary diluents played a crucial
role on the phase diagram changes of PPS/DPK/BZ. When the
Journal of Membrane Science 556 (2018) 107–117
M-d10 M-d15 M-d20 M-d25
69.4 ± 4.2 73.9 ± 3.5 71.3 ± 3.8 67.5 ± 4.3
165.2 138.6 124.1 132.5
201.2 ± 3 206.8 ± 2 215.7 ± 4 209.4 ± 3
interaction between polymer and diluents was poor, polymer casting
solution would directly enter a metastable or an unstable region to
undergone the liquid-liquid (L-L) phase separation [44]. When the in-
teraction between polymer and diluent was strong, the solid-liquid (S-L)
phase separation would take place in accompany with L-L phase se-
paration [37]. As shown in Fig. 3b, the interaction parameter between
PPS and diluents linearly reduced as DPK/BZ ratio increased. The
smaller value of χ presented the better interaction between PPS and
diluent [45]. Thus, the interaction between PPS and mixed diluents
became stronger with the increase of DPK content.
3.2. Morphologies of PPS porous membrane
(2) fluence on the membrane micro-structure evolution. When the tem-
perature gap between Tcloud and Tc is too large, especially in the case of
the fast cooling rate, the phase separation through spinodal decom-
position in the unstable region and the sponge pore structure is ob-
tained [46]. When the temperature gap between Tcloud and Tc is too
small, the membrane structure easily changed into spherulitic structure
[47].
The effects of DPK/BZ weight ratio on membrane cross-section
structures were shown in Fig. 4. As shown in Fig. 4a-2, the cross-section
structure of M-d0 was honeycomb pores which was the typical structure
formed by L-L phase separation system. As DPK content increased, a bi-
(3)
continuous network structure was obtained in M-d15 (Fig. 4c-2). As
shown in Fig. 3a, the Tcloud of the sample with 25 wt/75 wt of DPK/BZ
was close to its Tc, therefore the L-L phase separation had no enough
time to accomplish before the crystallization of PPS took place.
Therefore, both spherulitic structure and branching structure were
observed in Fig. 4e-2, which were attributed to the combination of L-L
phase separation and the crystallization of PPS. The porosity, average
pore size and thickness of PPS membranes were shown in Table 1. The
porosity firstly increased and subsequently decreased with the increase
of DPK concentration, and the largest porosity was established in M-
d15. The closed honeycomb pores resulted in the low porosity, but the
good connectivity of bi-continuous network pore structure led to the
high porosity. However, much more DPK in diluents would result in
membrane porosity decline, for example, M-d20 and M-d25. This was
mainly attributed to the crystallization of PPS polymer and the densi-
fication of membrane structure. The thickness of all the membranes was
around 210 µm, because they were all manually scraped by the same
casting bar. In summary, the controllable membrane structure can be
(4)
obtained by DPK/BZ ratio.
(5) The kinetic factor and thermodynamic factor were another two
important factors that influenced membrane structure. The top surface
(6)
and bottom surface structures of PPS membranes could be observed in
Fig. 5. As shown in Fig. 5, the porosity and roughness of bottom surface
of PPS membranes were much higher than those of top surface. The
difference between top surface and bottom surface resulted from the
different cooling rate. When casting solution was immersed in the
coagulation bath, the top surface (cold water side) of the membrane
directly contacted with the cold water, but the bottom surface (hot steel
side) of membrane contacted with the hot stainless steel plat, which
caused the cooling rate near the bottom surface of PPS membrane much
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T. Fan et al. Journal of Membrane Science 556 (2018) 107–117

Fig. 5. SEM images of the surfaces of PPS membranes (a: M-d0, b: M-d10, c: M-d15, d: M-d20, e: M-d25; 3: the top surface ×4000, 4: the bottom surface ×4000).

lower than that near the top surface of PPS membrane [48]. Therefore,
the prolonged primary stage of spinodal decomposition near the bottom
surface of PPS membrane was benefited the higher porosity and larger
pore size [49,50]. As shown in Fig. 5a-4, the larger pores were observed
in M-d0. As the DPK/BZ weight ratio increased to 15/85 in mixed di-
luents, M-d15 had a uniform branch-like surface structure without
larger pore existence (Fig. 5c-4). Because the temperature gap between
Tcloud and Tc of M-d0 was larger than that of M-d15 (Fig. 3), M-d0 had
more time for L-L phase separation than M-d15, leading to larger vo-
lume fraction of lean-polymer phase, which resulted in the structure
with larger pores. As the DPK/BZ weight ratio increased to 25 /75 in
diluent mixture, a spherulitic structure was observed, as shown in

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T. Fan et al.
Fig. 6. The three-dimensional AFM surface images of the PPS membranes: (a) M-d0, (b) M-d10, (c) M-d15, (d) M-d20, (e) M-d25.
Fig. 7. (a) Water contact angle of bottom surface of different PPS/diluent mixture membranes, (b) variation of water droplet on the surface of the membrane M-d15.
Fig. 5e-4.
The three-dimensional images of membrane bottom surfaces were
shown in Fig. 6. Obviously, the surface roughness of samples firstly
increased and subsequently decreased with DPK concentration increase,
and M-d15 reached the maximum roughness. In the range of the
scanned area (8 µm × 8 µm), the average surface roughness Ra of M-d0,
M-d10, M-d15, M-d20 and M-d25 membranes were 93, 125, 188, 164,
and 137 nm, respectively.
3.3. Wettabilities of PPS membranes
Hydrophobicity played the key role in membrane distillation
[51,52]. What's more, the surface roughness was closely linked with the
hydrophobic property, and the greater surface roughness could result in
the higher hydrophobicity [53]. The water contact angles of top surface
of PPS membranes were shown in Fig S2. The water contact angles of
PPS membrane top surface firstly increased from 90.3° to 108.7° then
decreased to 95.3° with DPK/BZ weight ratio increase. The water
contact angles of bottom surface of PPS membranes were shown in
Fig. 7a. The water contact angle of PPS membrane bottom surface
firstly increased from 125.1° to 142.6° then decreased to 133.5° with
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Journal of Membrane Science 556 (2018) 107–117
DPK/BZ weight ratio increase. The result showed that M-d15 achieved
the maximum water contact angle of 142.6° because its special branch
micro/nano-porous structure can effectively enhance membrane wet-
ting behavior [54]. Furthermore, the branch porous surface can reduce
the solid-liquid contact area and capture much more gas (Fig. 8a) [55].
It is similar to the bottom surface structure of Berberis thunbergii var.
atropurpurea Chenault leaf which is excellent hydrophobic, as shown in
Fig. 8b. As seen in Fig. 7b and Movie S1, after the water droplet stood
on the membrane surface for 28,241 ms, the water droplet remained at
142.6°. Most importantly, the membrane M-d15 exhibited the strong
hydrophobicity not only to salt water (142.4°), but also to other solu-
tions having different pH values or even to strong acid and alkaline
solutions, as shown in Fig. 8c.
Supplementary material related to this article can be found online at
http://dx.doi.org/10.1016/j.memsci.2018.03.084.
3.4. Chemical stabilities of PPS membranes
The SEM images of M-d15 bottom surfaces and cross-sections
treated with acid, alkali and polar solvent were shown in Fig. S3. The
membrane thickness of M-d15 treated with acid, alkali and polar
T. Fan et al.
Fig. 9. Mechanical properties of different PPS membranes.
solvent was shown in Table S1. The variation of water contact angles of
M-d15 with time under harsh chemical conditions were shown in Fig
S4. After membranes were treated with corrosive solutions and organic
solvents, the membrane morphologies (surfaces and cross-sections) and
thicknesses had almost no change, and the hydrophobicity remained
unchanged. Those results indicated that PPS membrane exhibited the
superior performance against strong acid, strong alkaline and polar
organic solvent resistance. Thus, PPS membranes had a great potential
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Journal of Membrane Science 556 (2018) 107–117
Fig. 8. (a) Diagrams illustrate the effect of
surface structure of M-d15 on the hydro-
phobicity; (b) (1) the picture of Berberis
thunbergii var.atropurpurea Chenault leaves
and (2) SEM photograph of the bottom surface
of Berberis thunbergii var.atropurpurea
Chenault leaf; (c) photograph of different li-
quid droplets on the M-d15 surface (white: salt
water; red, orange, pink, green, blue: water
pH = 1, 3, 7, 10, 13, respectively.). (For in-
terpretation of the references to color in this
figure legend, the reader is referred to the web
version of this article.)
utilization in water treatment under the harsh environment conditions.
3.5. The mechanical properties of porous membranes
The micro-structure of membrane played the key role on the me-
chanical properties. The mechanical properties of PPS membranes were
shown in Fig. 9. Breaking strength firstly decreased from 3.75 MPa of
M-d0 to 2.89 MPa of M-d15 with DPK concentration increase because
the increased DPK concentration resulted in the higher membrane
porosity to reduce the breaking strength [56]. However, the breaking
strength increased from 2.89 MPa of M-d15 to 3.12 MPa of M-d25
which was attributed to the denser pore structure was shown in
Fig. 4(2). The elongation-at-break also decreased from 13.56% of M-d0
to 10.32% of M-d15, and then slowly increased to 10.90% of M-d25.
3.6. Permeabilities of PPS membranes
The contact angle and surface pore size of membrane played the two
key roles on the LEP. As shown in Fig S5, the LEP of the prepared PPS
membranes firstly increased and subsequently decreased with the in-
crease of DPK concentration. And all the LEP value of prepared mem-
branes exceeded 0.4 MPa, which was far higher than the operating
pressure (0.1 MPa), therefore water could not permeate through the
membrane [57].
3.7. VMD desalination performances
The prepared PPS membranes were tested in the VMD process.
Because the bottom surface contact angles of the prepared PPS
T. Fan et al.
Fig. 10. Variations of permeate flux (a) and salt rejection (b) as a function of
different feed temperature and DPK/BZ ratio.
Fig. 11. Long-time VMD tests of M-d15 (3.5 wt% NaCl and 10 wt% NaOH so-
lution as the feed, feed temperature: 80 °C).
membranes were much higher than that of the top surface, we selected
the bottom surface of PPS membranes to be in contact with the feed
solution in VMD tests. In the process of membrane distillation, the
temperature of feed solution was heated from 70 to 90 °C. The effects of
feed solution temperature and DPK/BZ weight ratio on the permeate
flux were exhibited in Fig. 10a. After testing several hours, all obtained
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Journal of Membrane Science 556 (2018) 107–117
values were stable fluxes. The permeate flux of all membrane samples
raised as the feed solution temperature increase, but the permeate flux
enhanced firstly then declined with the DPK content increased, and
membrane M-d15 achieved the maximum permeate flux of 22.8 L m−2
h−1. From M-d0 to M-d15, the increase of permeate flux was attributed
to the improvement of membrane porosity. Bi-continuous network
structure was well interconnected, which resulted in the high perme-
ability [58]. As DPK content further increase, the spherulitic structure
appeared, which resulted in the decline of permeate flux. In summary,
the variation of membrane structure was the main reason for the
membrane performance.
The effects of feed solution temperature and DPK/BZ weight ratio
on the salt rejections were shown in Fig. 10b. The salt rejections of all
prepared membranes achieved 99% during the test. Especially, the
membrane M-d15 achieved 99.99%, and the exudate conductivity was
less than 5 μs cm−1 after 10 h continuous test (Fig. S6). Berberis thun-
bergii var. atropurpurea Chenault leaf-like surface structure of M-d15
made the water contact angle reach 142.6° and the LEP reach 0.65 MPa,
and its excellent hydrophobicity resulted in the highest separation ef-
ficiency. In summary, the high hydrophobicity of membrane is neces-
sary for VMD because it is one of the main factor to influence LEP and
pore wetting, which plays the key role on salt rejection.
To test the durability property of prepared PPS membrane in the
corrosive water, a mixed aqueous solution of 3.5 wt% NaCl and 10 wt%
NaOH was used as the feed solution in VMD experiments. As shown in
Fig. 11, the permeate flux decreased slightly, which was mainly due to
the concentration polarization to result in a decrease in the vapor
pressure differential across the membrane [59,60]. The salt rejection of
M-d15 was still more than 99.9% after continuous operation of 10 h.
These results indicated that PPS membrane possessed the superior
performance against strong alkaline and it exhibited a great potential
and feasibility for their utilization in MD process under corrosive water
treatment conditions.
Moreover, the comparison of the membrane distillation perfor-
mance obtained in this study with the other membranes in the literature
was listed in Table 2 [61–64]. These result illustrated that not only the
permeate flux but also the salt rejection of the obtained PPS membrane
was much higher than that of the reported membranes.
4. Conclusions
PPS hydrophobic porous membranes were prepared from the mixed
diluent of DPK and BZ via TIPS. The DPK/BZ weight ratio in mixed
diluent played a decisive role in the membrane structure evolution and
performance. As the DPK/BZ weight ratio increased, the interaction
between PPS and diluents became stronger, and the structure of
membranes changed from honeycomb, bi-continuous network to
spherical particle via L-L phase separation. The variation of membrane
structure directly led to the different membrane performance. The bi-
continuous network structure of membrane M-d15 (DPK/BZ weight
ratio of 15/85) exhibited the excellent permeability, and the Berberis
thunbergii var. atropurpurea Chenault leaf-like surface structure dis-
played the strong hydrophobicity. In the VMD process, the maximum
permeate flux of M-d15 achieved 22.8 L/m−2 h−1 and the salt rejection
reached 99.99%. Most importantly, PPS membranes possessed the su-
perior chemical resistance and exhibited the excellent stability in cor-
rosive water desalination experiments. Therefore, PPS membrane was
not only a new membrane for seawater desalination but also expected
to accelerate its practical application in different fields (such as oil-
water separation, solvent resistant nanofiltration and pervaporation
separation of ethanol/toluene and methanol/toluene mixtures etc.) in
the next few years.
T. Fan et al. Journal of Membrane Science 556 (2018) 107–117

Table 2
Permeate flux and NaCl rejection in this study compared to other membranes in VMD processes.
Membrane code Feed solution Feed (°C) Vacuum (kPa) Permeation flux (L/(m2 h)) NaCl rejection (%) Ref.

PVDF-SiO2 flat-sheet 3.5 wt% NaCl 27 94.8 2.9 99.9 [61]

PPESK hollow fiber membrane 5 g/L NaCl 40 78 3.7 94.6 [62]
PVDF flat-sheet 3.5 wt% NaCl 80 15 11.8 97.0 [63]
PVDF flat-sheet 3.5 wt% NaCl 80 81.5 12.5 99.7 [64]
PPS flat-sheet M-d15 3.5 wt% NaCl 80 80 14.7 99.9 This work
PPS flat-sheet M-d15 3.5 wt% NaCl 90 80 22.8 99.9 This work

Acknowledgments Desalination 233 (2008) 19–31.

The authors are grateful for the financial support from National
Natural Science Foundation of China (Nos. 21676202 and 21376177)
and Tianjin Natural Science Foundation of China (no. 15JCZDJC7000).
This work is also supported by China National Textile and Apparel
Council (J201406) and China Petroleum Chemical Co Technology
Development Project (208068, 201100, 215038 and 216090).
Appendix A. Supplementary material
Supplementary data associated with this article can be found in the
online version at http://dx.doi.org/10.1016/j.memsci.2018.03.084.
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