Journal of Environmental Chemical Engineering 8 (2020) 103921

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Journal of Environmental Chemical Engineering

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Recycled PET as a PDMS-Functionalized electrospun fibrous membrane for T

oil-water separation
Hoan Ngoc Doana, Phu Phong Voa, Kohei Hayashib, Kenji Kinashic,*, Wataru Sakaic,
Naoto Tsutsumic
a
Doctor’s Program of Materials Chemistry, Graduate School of Science and Technology, Kyoto Institute of Technology, Matsugasaki, Sakyo, Kyoto 606-8585, Japan
b
Master's Program of Innovative Materials, Graduate School of Science and Technology, Kyoto Institute of Technology, Matsugasaki, Sakyo, Kyoto 606-8585, Japan
c
Faculty of Materials Science and Engineering, Kyoto Institute of Technology, Matsugasaki, Sakyo, Kyoto 606-8585, Japan

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

Editor: Yunho Lee In recent years, low-cost and effective technologies for oil-water separation have been highly desired due to an
Keywords: increase of oily wastewater and frequent oil spill accidents. This study demonstrates a cost-effective and sus-
Electrospinning tainable preparation of flexible fibrous membranes with high oil-water separation performance using recycled
Polyethylene terephthalate polyethylene terephthalate (rPET). The rPET fibrous membrane was prepared via electrospinning; in the fol-
Polydimethylsiloxane lowing step, the rPET membrane was dip-coated with polydimethylsiloxane (PDMS) to improve the water in-
Waste recycling trusion pressure and anti-water-fouling property of the rPET fibrous membrane. The effect of PDMS con-
Oil-water separation centration on the membrane morphology, surface chemistry, thermal and mechanical properties, surface
wettability and oil-water separation performance was evaluated. The membranes are superoleophilic with an oil
contact angle of 0° and exhibit excellent anti-water-fouling properties. The PDMS-functionalized rPET mem-
branes can effectively separate various oil-water mixtures driven by gravity, with a high flux (∼ 20,000 L m−2
h-1) and a high separation efficiency (> 98 %) for up to ten cycles and thus has potential industrial application.

1. Introduction effective, efficient, and sustainable methods to separate and recycle oil-
water streams is still highly in demand. Previous studies showed that
Oil-water separation has recently attracted much attention due to an using waste polymers base fibrous membrane for water-oil separation is
increase of waste from the oil industry and the occurrence of oil spills, the promising approach. Sow et al. fabricated waste polystyrene fibers
which has caused adverse impacts to both the ecosystem and human by solution blow spinning and successfully applied them towards oil-
beings [1,2]. Recently, great efforts have been devoted to developing water separation [20]. In addition, electrospun membranes fabricated
efficient oil-water separation techniques for oily wastewater treatment, from waste cigarette for application on oil-water mixture and emulsions
including dispersants [3], adsorption [4–6], burning [7], skimmers [8] separation were produced by Liu and co-worker [21].
and membrane separation [9]. Among these techniques, fibrous mem- In addition to oil spill pollution, plastic bottle waste is a serious
branes for oil-water separation fabricated by electrospinning are concern for the ocean. Most plastic bottles are made from poly(ethylene
emerging as good candidates due to their high flexibility and high se- terephthalate) (PET), a synthetic polymer with high environmental
paration performance [10–12]. Various polymers, such as poly- resistance that is still being used for water and soft drinks. Therefore,
vinylidene fluoride [13], polyimide [14,15], polyurethane [16], poly(ε- the discarded PET bottles are resistant to decomposing naturally in the
caprolactone) [17], polylactide [18], and polysulfonamide/poly- ocean due to their durability, and as a result, this problem also leads to
acrylonitrile [19] have been widely used for preparing flexible elec- severe environmental pollution [22,23]. For this reason, waste man-
trospun fibrous membranes for oil-water separation. However, the cost agement and recycling technology for PET bottles is an important re-
of producing these membranes is not always economically viable be- search field for environmental conservation [24,25]. The profit in-
cause these virgin polymers have a high and stable cost. The materials volved in recycled PET (rPET) production is relatively low because the
used in the previous studies were virgin polymers, which could lead to rPET bottles are mainly recycled to make low-cost products, such as
another environmental issue [37]. With an increasing level of attention sheets, stationery, and detergent bottles. Therefore, there is a demand
focused on preserving the environment, the development of cost- for a method by which to make value-added rPET products that offset

⁎
Corresponding author.
E-mail address: kinashi@kit.ac.jp (K. Kinashi).

https://doi.org/10.1016/j.jece.2020.103921
Received 9 January 2020; Received in revised form 28 March 2020; Accepted 30 March 2020
Available online 25 April 2020
2213-3437/ © 2020 Elsevier Ltd. All rights reserved.
H.N. Doan, et al. Journal of Environmental Chemical Engineering 8 (2020) 103921

the cost of recycling and encourage the collection of PET bottle waste. 22 ± 2 °C, respectively, was maintained by monitoring with a hygro-
Applying rPET fibrous membranes to an oil-water separation process thermograph placed inside the electrospinning chamber. The resulting
can be an alternative to using a virgin polymer, as electrospinning fibrous membranes were placed in a vacuum oven for 2 h at 50 °C to
waste PET for a cost reduction can be expected to be a powerful re- remove any retained solvents.
cycling method for a sustainable society. Furthermore, using rPET as a
separation membrane could lead to another environmental benefit be- 2.3. PDMS modification
cause it can reduce the released of the plastic to the environment. Re-
cently, a number of studies have examined the production of electro- Polydimethylsiloxane (PDMS)-functionalized rPET membranes
spun rPET nanofibrous membranes for filtration operations. Strain et al. (rPET@PDMS) were prepared using a dip-coating method. A PDMS
fabricated a tough nanofibrous membranes from rPET/DCM/TFA so- prepolymer was blended with a cross-linker at a constant weight ratio
lutions for smoke filtration [26]. An antimicrobial rPET nanofibrous of 10:1. The as-prepared rPET membranes were cut into a round shape
membrane used for water filtration was also produced by Zander et al. with a diameter of 10 mm and were immersed in a PDMS/hexane so-
[27]. However, the oil-water separation performance of the electrospun lution with varying PDMS concentrations (1, 2, 4, and 8 wt%) at 25 °C
rPET has not yet been reported in the literature. for 2 h. After the dip-coating process, the archived fibrous membrane
In this study, we introduce a facile and sustainable technology to was dried for 5 h in a vacuum oven at 50 °C. The obtained membranes
produce a superoleophilic and underoil superhydrophobic membrane were denoted as rPET@PDMS_1, rPET@PDMS_2, rPET@PDMS_4, and
using rPET for oil-water separation. The rPET membranes were fabri- rPET@PDMS_8, respectively.
cated from rPET/DCM/TFA solutions. The used solvents can be col-
lected using a vapor condensation system and can be recycled in order 2.4. Membrane characterization
to reduce the release of solvents to the environment, which makes the
product more cost effective and environment-friendly. Due to the che- Morphology and energy dispersive X-ray spectrometry (EDX) for the
mical properties of PET, the as-spun rPET membrane shows a low water membranes were studied by a field-emission scanning electron micro-
intrusion pressure and a lack of anti-water fouling, which are very scope (FE-SEM) (JEOL-7600, JEOL Ltd., Japan) equipped with an
important for a membrane used for oil-water separation. The as-spun Oxford energy dispersive X-ray spectrometer. The membranes were
rPET fibrous membrane was dip-coated with polydimethylsiloxane sputter-coated with a 30 nm thick layer of palladium and observed
(PDMS), which has a low surface energy property, enhancing the anti- using FE-SEM at an accelerating voltage of 5 kV. Fiber diameters were
water fouling properties and overcoming the above weaknesses. The analyzed using SEM images and image processing software (ImageJ).
wettability and water intrusion pressure of the rPET fibrous membrane The surface roughness of the membranes was determined using a
can be manipulated by controlling the amount of PDMS in the dipping noncontact laser profilometry analysis method mounted on a 3D laser
solution. The effects of PDMS concentration on morphology and scanning microscope (VK-2000, Keyence Co., Japan). IR spectra of the
structure, chemical composition of the membrane surface, thermal membranes were recorded using an FT-IR spectrophotometer (FT/IR
properties, mechanical properties, and oil-water separation perfor- 4700, Jasco Co., Japan) with a universal attenuated total reflectance
mance were investigated. accessory (ATR PRO ONE equipped with a diamond prism, Jasco Co.,
Japan). The chemical compositions of the membrane surfaces were
2. Materials and methods investigated using an X-ray photoelectron spectrometer (JEOL 9010,
JEOL Co., Japan). Contact angle analysis was conducted using a
2.1. Materials Phoenix 300 contact-angle system (Kromtek Co., Malaysia) at 20 °C,
and the obtained images were analyzed with analysis software
Recycled PET pellets from postconsumer PET water bottles (ImageJ). For the analysis, the rPET@PDMS membranes were placed on
(CR–8816) were kindly provided by Dr. Kazushi Yamada (Advanced a glass substrate, water was used for the water contact angle (WCA) and
Fibro-Science, Kyoto Institute of Technology, Kyoto, Japan). hexane was used for the oil contact angle. Measurements were carried
Trifluoroacetic acid (TFA), dichloromethane (DCM), hexane, ethylene out on the membrane surfaces at room temperature in an opened
tetrachloride, carbon tetrachloride and bromobenzene were purchased chamber. The volume of the sessile drop was maintained at 3 μL. The
from Wako Co., Osaka, Japan. A PDMS prepolymer and cross-linker sample membranes were placed in a hexane bath during contact angle
(Sylgard 184) were manufactured by Dow Corning Co., USA. All of the measurement to evaluate the underoil hydrophobicity. The average
chemicals were used as received without further purification. contact angle values were obtained by measuring at least five different
measurement points across the sample surface. The water intrusion
2.2. Electrospinning pressure value was measured by a homemade testing system of our own
design, as shown in Fig. S1. The thermal properties of the resulting
An rPET solution with a concentration of 12 wt% was prepared by fibers were studied using differential scanning calorimetry (DSC).
dissolving rPET pellets in a solvent mixture of trifluoroacetic acid (TFA) Thermograms were obtained using a TA Instruments Q200 calorimeter
and dichloromethane (DCM) (7:3 w/w). The solution was mixed for (TA Instruments Japan Inc., Tokyo, Japan) with a heating rate of 10 °C
30 min using a planetary centrifugal mixer (ARE-310, Thinky Co., min−1 in a nitrogen atmosphere. The thermogravimetric analysis (TGA)
Tokyo, Japan) at 2000 rpm and then degassed at 2200 rpm for 90 s. The curves and the first derivative of the TGA curve (differential thermo-
prepared solutions were kept in a constant-temperature shaker (MMS-1, gravimetric (DTG) curve) were obtained by a TGA machine (Discovery
Eyela Co., Japan) at 25 °C to obtain homogeneous solutions. The rPET TGA, TA Instruments) with a heating rate of 10 °C min−1 in a nitrogen
nanofibrous membranes were prepared using a build-up electrospin- atmosphere. The mechanical properties of the samples were char-
ning system of our own design. During the electrospinning process, the acterized using a universal tensile testing machine (TENSILON
feed rate of the rPET solution was kept at 0.5 mL h−1 by a syringe pump RTF–1210, A&D Co., Japan) (crosshead speed: 1 mm min−1, load cell:
(KDS-100, KD Scientific Inc., Massachusetts, USA). A high voltage of 100 N). The fibrous samples were cut out in the form of miniaturized
15 kV generated from a high voltage power supply (HVU-30P100, dog bone-shaped specimens (type 5B in BS ISO 527: 2012) using a
MECC Co., Japan) was applied to a 27 G needle with an inner diameter cutting blade. Then, the specimens were mounted onto a paper frame
of 0.20 mm. The distance between the needle and fiber collector was using double-sided tape. The thickness of the testing specimen was
fixed at 12.5 cm. A rotating drum covered by a stainless-steel mesh (No. measured using a micrometer screw gauge (Mitutoyo 406−250,
10) was used as a fiber collector with a constant rolling speed of Mitutoyo, Japan). Tensile tests were performed in an atmosphere with a
120 rpm. The relative humidity and temperature of 30 ± 5% and temperature and relative humidity of 20 ± 2 °C and 35 ± 5%,

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respectively. The tests were performed using at least five specimens for morphology and structure of the as-spun and PDMS-modified rPET
each fibrous membrane. membranes were investigated. Fig. 1a‒e shows the morphology and
structure of the as-spun and PDMS-modified rPET membranes. The
2.5. Oil-water separation experiment rPET electrospun fibers have a smooth surface and a low degree of
interconnected network structure with a fiber diameter of
The separation experiments were performed using a dead-end fil- 710 ± 249 nm (Fig. S2). The formation of the interconnected network
tration apparatus. The obtained modified rPET@PDMS membrane was structure in the as-spun rPET sample could be assigned to the in-
cut in a round shape with a diameter of 25 mm and then fixed between complete evaporation of the used solvents [31,32]. When the rPET
the filter holder (KGS-25, Advantec Co., Japan) with a stainless-steel membrane was modified with a PDMS solution of 1 wt%, a slight
supporter. Before conducting the oil-water separation, the membranes change in the morphology of the membrane with increased inter-
were prewetted with the corresponding oil. Separation tests were con- connected bonding structure was observed, as shown in Figs. 1b and
ducted by pouring 40 mL of the oil/water mixture (volume ratio = 1/1) Fig. S2. In the case of a PDMS concentration of 2 wt%, some adhesive
into the upper tube, and the oil was collected in a beaker at the bottom areas, in which the voids between rPET fibers were filled by PDMS,
of the filter holder. The flux through the membrane was calculated appeared on the membrane surface. With a further increase in PDMS
using the following equation: concentration, the adhesive structure among the fibers increased sig-
V nificantly. When the PDMS concentration was further increased to 4 wt
F= %, the adhesive areas became larger than that of the rPET@PDMS_2.
At
When the PDMS concentration was finally increased to 8 wt%, the
where F is the flux, V is the volume of the permeate oil through the porous structure of the membrane was greatly decreased, and the voids
membrane during time t, and A is the effective contact area of the between the fibers were almost filled with PDMS.
membrane and the mixture. The separation efficiency was calculated The roughness of the membrane surface was further investigated via
using the following equation: a noncontact laser profilometry analysis method. Fig. 1f demonstrates
M the corresponding Ra values of the membranes. The detailed optical
η= × 100%
M0 profilometry images were demonstrated in Fig. S3. The as-spun rPET
membrane exhibited the highest Ra value of 3.4 μm, indicating a rela-
where η is the separation efficiency, M is the weight of the oil collected tively rough surface. As expected, the corresponding Ra value decreased
in the beaker after separation and M0 is the initial weight before the to 2.7 μm when the membrane was modified with 1 wt% PDMS solu-
separation. Three samples of each fibrous membrane were tested. To tion, which was mainly due to the interconnection between fibers
determine the recycling ability of the functionalized rPET membrane, formed by the PDMS layer. The roughness gradually decreased with a
the tests were repeated 10 times without any treatment between the further increase in the concentration of the PDMS, which resulted from
cycles. The oil-water separation test was set up following a published the increase in the amount of adhesive area formed by PDMS. Thus, the
report [28]. rPET@PDMS_2 and rPET@PDMS_4 exhibited Ra values of 2.3 and
2.0 μm, respectively, which corresponded to the results from the SEM
3. Results and discussion characterizations. With a further increase in PDMS concentration, there
was no obvious difference in Ra for rPET@PDMS_4 and rPET@PDMS_8.
3.1. Morphology and surface chemical composition The presence of the PDMS layer on the functionalized rPET mem-
brane was investigated by attenuated total reflectance Fourier trans-
Previous studies demonstrated that the oil-water separation and form infrared (ATR FT-IR) measurements. Fig. 2a shows the ATR FT-IR
surface wettability of the electrospun membranes were strongly de- spectra of the rPET membranes before and after modification with
pendent on the fiber diameter, porosity, pore size, surface chemistry, different amounts of PDMS. The differences in terms of transmittance at
and surface roughness of the membranes [29,30]. Therefore, the

Fig. 1. SEM images of (a) as-spun rPET, (b) rPET@PDMS_1, (c) rPET@PDMS_2, (d) rPET@PDMS_4, and (e) rPET@PDMS_8. (f) The Ra values of the membranes
(insets: the corresponding optical profilometry images).

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H.N. Doan, et al. Journal of Environmental Chemical Engineering 8 (2020) 103921

Fig. 2. (a) ATR FT-IR spectra of the rPET@PDMS nanofibrous membranes obtained with various PDMS concentrations; (b) ATR IT-IR spectra of the rPET@PDMS_2,
PDMS_Bulk, PDMS_Prepolymer and PDMS_Crosslinker.

2965, 2905, 1262, 1097, 1017, 845 and 801 cm−1 of the rPET@PDMS the rPET fibers functionalized with PDMS concentrations of 2, 4, and
membranes are attributed to the functional groups of PDMS [33–35]. 8 wt% show approximately 23–24 %.
These bands are assigned to CeH asymmetric stretching (2965 cm−1), The changing fiber surface chemical composition was further in-
CeH stretching (2905 cm−1), CeH bending (1262 cm−1), Si–O–Si vestigated by an XPS narrow spectrum at C 1s for the as-spun and
asymmetric stretching (1097 cm−1), wagging vibrations of –(CH2)– modified rPET membranes. As shown in Fig. 4, a broad C 1s spectra
(1017 cm−1), CeH rocking (845 cm−1), and Si–C stretching centered at 285.0 eV could be decomposed into 285.0 eV, 286.7 eV and
(801 cm−1). It should be noted here that the ATR FT-IR result of the 289.2 eV, and these peaks corresponded to the C–H/C–C, C–O, and
rPET@PDMS_2 does not show a band at 2163 cm−1 associated with the O–C=O binding energies, respectively. The rPET membrane coated
presence of the Si–H group in the crosslinker, which indicates that the with the 1 wt% PDMS solution (rPET@PDMS_1) demonstrated that the
PDMS prepolymer and crosslinking agent are completely polymerized, peak intensity of C–O and O–C=O binding energies greatly decreased
as shown in Fig. 2b. in comparison with that of the as-spun rPET membrane, as shown in
The chemical composition of the PDMS layer on the rPET fibers was Fig. 4b. With a further increase in PDMS concentration, the signals
further evaluated by XPS. Fig. 3a shows the XPS spectra of the rPET corresponding to the CeO and OeC=O binding energies disappear in
membrane after modification with different amounts of PDMS, in which all the XPS narrow spectra, indicating that the surfaces of the rPET
the C 1s and O 1s signals appear at 285.0 eV and 533.0 eV, respectively. membranes were fully covered with PDMS.
In addition, Si signals also appear in the PDMS-functionalized rPET The distribution of PDMS on the membrane was evaluated by using
membranes, as seen at binding energies of 100.5 eV and 152.5 eV. This EDX Si mapping, as shown in Fig. S4. As a result, a homogeneously
result indicates that the surface of the rPET fibers was modified by dispersed Si content on the fibers was observed.
PDMS. The detailed elemental composition of the rPET membrane be-
fore and after PDMS functionalization was calculated, as shown in
Fig. 3b. As a result, taking the rPET fibers that were modified by the 3.2. Thermal properties
PDSM solution with 1 wt% as an example, the relative percentage of Si
on the membrane increased significantly from nearly 0% to 22.2%. The effect of PDMS concentration on the thermal properties of the
However, even if the treatment concentration of PDMS was increased, rPET membranes was investigated by using DSC and TGA analysis, as
the percentage of Si was almost constant, as shown in Fig. 3b. In ad- shown in Fig. 5. In the DSC thermograms, an endothermic peak cor-
dition, the percentage of Si was almost the same as the elemental ratio responded to an enthalpy relaxation that appeared at approximately 80
of a bulk PDMS (Si: 25.3 %); accordingly, all of the Si percentages for °C for each sample, which was attributed to the presence of a meso-
morphic phase (oriented amorphous phase) in the fibers [26,36]. The

Fig. 3. (a) Survey-scan XPS spectra of rPET@PDMS nanofibrous membranes obtained from various PDMS concentrations and (b) detailed elemental composition of
the rPET membrane before and after PDMS functionalization.

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H.N. Doan, et al. Journal of Environmental Chemical Engineering 8 (2020) 103921

Fig. 4. C 1s spectra analysis of the as-spun rPET, bulk PDMS and rPET@PDMS fibrous membranes obtained with various PDMS concentrations.

mesomorphic phase would be formed when the fibers were stretched decrease in weight loss in the range of 350 °C-510 °C with a DTG peak at
during the electrospinning process and/or the heating treatment after 446 °C, and instead an increase of DTG peaks at 531 °C and 617 °C were
the dip-coating process at 50 °C. Furthermore, the presence of the PDMS measured. The rPET@PDMS samples were completely degraded at ap-
layer on the rPET fibers could prevent the heating effect on the rPET, proximately 700 °C.
causing an increase in the cold crystallization temperature (Tc) of the
rPET@PDMS samples.
The effect of PDMS concentration on the thermal degradation of 3.3. Wettability
rPET@PDMS membranes was evaluated using TGA, as described in
Figs. 5b and S5. The results show that the pyrolysis of the as-spun rPET A highly selective wettability is a crucial factor that significantly
sample started at approximately 350 °C. The sample was completely affects the separation performance of the membrane [11,30,37,38].
degraded at 510 °C with a peak at 446 °C and producing residue with an Therefore, the wettability of the as-spun rPET and rPET@PDMS mem-
amount of 15 wt%. Meanwhile, the rPET@PDMS samples show a higher branes was examined. The effect of PDMS concentration on the WCA
thermal stability with two more peaks at 531 °C and 617 °C in the DTG and water intrusion pressure was studied. Fig. 6a shows that the as-spun
curves, indicating the presence of PDMS on the sample with a higher rPET membrane demonstrates a high WCA of 137.6°, which is much
degradation temperature. The TGA and DTG curves of the as-spun rPET higher than that of the pristine PET film. The increase in the WCA of the
and rPET@PDMS membranes show different shapes with different rPET membrane was attributed to the increase of surface roughness,
PDMS concentrations, which indicates that different amounts of PDMS which led to the trapping of air pockets under the water droplet. The
were incorporated into the rPET fibrous membrane. When the PDMS highest WCA of 149.7° was found with the rPET@PDMS_2 sample. The
content increased, the TGA curves of the rPET@PDMS samples show a increased WCA of the modified samples would be due to the presence of
PDMS with a low surface energy. However, when the PDMS

Fig. 5. (a) DSC thermograms and (b) TGA curves of the as-spun rPET and rPET@PDMS membranes obtained with various PDMS concentrations.

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Fig. 6. (a) WCA and intrusion pressure of the rPET@PDMS membrane; (b) oil contact angle and underoil WCA of the rPET@PDMS membrane; (c) dynamic
measurement of water adhesion of the as-spun rPET and rPET@PDMS_1 samples; (d) mobility of the water droplet on the TCE-wetted rPET@PDMS_1 membrane.

concentration further increased, the WCA of the rPET@PDMS_4 and the case of the rPET membrane functionalized with the PDMS, the
rPET@PDMS_8 decreased to 147.6° and 147.3°, respectively. As dis- membrane showed excellent anti-water-fouling performance. Fig. 6c
cussed above, the decreasing WCA for the samples with the PDMS and Video S3 show a water droplet that is forced to contact the rPET@
concentration increased from 2 wt% to 4 and 8 wt% would be caused by PDMS_1 membrane surface until an obvious deformation appears; then,
the decrease of surface roughness (increasing solid area fraction) caused it is lifted up and no deformation can be found in the shape of the water
by the formation of adhesive areas. The as-spun rPET membrane droplet. Accordingly, since the water droplet completely detached from
showed a low water intrusion pressure of 3.6 kPa. However, after the membrane surface, this indicates a high anti-water-fouling ability.
modifying with the 1 wt% PDMS solution, the water intrusion pressure To further demonstrate the anti-water-fouling property of the
significantly increased to 16.0 kPa. The water intrusion pressure of the membrane, the mobility of a water droplet on a trichloroethene (TCE)-
rPET@PDMS reached the highest value of 24.4 kPa when the PDMS wetted rPET@PDMS_1 membrane was evaluated. As shown in Fig. 6d
content further increased to 4 wt%. The water intrusion pressure de- and Video S4, a water droplet immediately moved down the membrane
pended on the surface wettability and pore size of the fibrous mem- even when the WCA was 101.0°, which meant that the oil-wetted
brane and could be expressed using the following equation [30,39]: rPET@PDMS membrane exhibited the features of robust anti-water
fouling and self-cleaning. The presence of TCE in the membrane led to
2γw 2γ cosθw
ΔPw = =− L the formation of a system called a slippery liquid-infused porous surface
r R (SLIPS), in which a lubricating liquid layer was introduced into a
where ΔPw is the water intrusion pressure, γw is the surface tension of micro/nanometer-scale porous structure. With the presence of a lu-
water in air, r is the curvature radius of meniscus, θw is the contact bricating liquid (oil), the SLIPS could repel a liquid (water) that is
angle of the liquid on the surface of fibers, R is the equivalent pore immiscible with the lubricating liquid (oil). The molecularly smooth
radius of the membrane. Using the above equation, the increase in and chemically homogeneous lubricating liquid layer provides ex-
water intrusion pressure of the rPET@PDMS was attributed to the in- tremely low sliding angle and contact angle hysteresis, leading to the
crease of WCA and the decrease of pore size. continuous movement of the water on the surface [40,41].
The obtained rPET@PDMS membrane exhibited superoleophilicity
with an oil contact angle of 0° in air and underoil superhydrophobicity 3.4. Mechanical properties
(UOWCA > 155°) (Video S1 and Fig. 6b). The results allowed the oil to
spread out and pass through the membrane while keeping the water In practical separation applications, the mechanical properties of
above the membrane. Although the as-spun rPET membrane was un- the rPET@PDMS membranes should be strong enough to withstand the
deroil superhydrophobic, the as-spun rPET could not prevent the ad- weight of the filtration liquid. The effect of the PDMS concentration on
hesion of oil on the membrane. Fig. 6c and Video S2 show that when a the tensile strength of the rPET@PDMS was evaluated, and the typical
water droplet comes into contact with the as-spun rPET membrane stress-strain curves are shown in Fig. 7a. The maximum tensile stress
surface, it is pinned onto the membrane surface, which indicates the and the elongation at break obtained from the curves are summarized
poor anti-water fouling of the unmodified rPET membrane. However, in in Fig. 7b.

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Fig. 7. (a) Stress-strain curves and (b) tensile properties of the PDMS-functionalized rPET membranes fabricated with different PDMS concentrations.

The results of the tensile test shown in Fig. 7a show that the is > 90°, thus the corresponding ΔPc is > 0 indicate that an external
breaking of the membranes occurred in two steps. In other words, a pressure must be applied to force the water through the membrane.
nonlinear region and a subsequent linear region in the stress-strain It was obvious that the flux was decreased gradually while the se-
curve indicated the interconnected structure of the rPET@PDMS paration efficiency stayed nearly the same when the used PDMS con-
membranes with a coexistence of connected/unconnected parts in the centration increased. The water permeation flux was as high as
membranes. The breaking of these membranes could be explained by a 19,584 ± 944 L m−2 h−1 and was achieved with the rPET@PDMS_1
two-step breaking mechanism [19]. Under an applied tensile stress, the sample with a separation efficiency of 98.5 %. However, the flux ob-
unconnected parts in the fibrous membrane could easily deform and tained from the rPET@PDMS_8 sample significantly decreased to
were forced to be aligned along the stress direction, resulting in non- 3730 ± 325 L m−2 h−1. The decrease in the flux could be attributed to
linear elastic behavior in the first region. When further stress was ap- the reduce of pore size and the porosity of the membrane. To compare
plied from that region, the strain curve transformed into a linear elas- with other adsorbents such as pristine foam, commercial adsorbent, and
ticity until breaking with a high linearity of 0.99, which could be waste polystyrene electrospun fibers (wPS) reported in recent work
attributed to the elongation of individual fibers. Overall, the increase of [42], the separation efficiency of the rPET@PDMS_1 membrane was
PDMS concentration in the dip-coating solution led to higher mechan- among the best. The rPET@PDMS_1 showed a separation efficiency of
ical properties of the rPET@PDMS membrane. The as-spun rPET 98.5 % while the pristine foam, commercial adsorbent, and wPS
membrane, which had the lowest interconnected bonding degree, de- showed 16 %, 44 %, and 84 %, respectively. Therefore, the rPET@
monstrated the lowest tensile strength of 3.4 ± 0.1 MPa and an elon- PDMS_1 can be a promising candidate for the oil spillage removal
gation at break of 273 ± 20 %. Furthermore, rPET@PDMS_8 exhibited compared to the commercial adsorbent. Table S1 shows the comparison
the highest mechanical properties with a tensile strength of of the oil-water separation performance of various electrospun fibrous
4.3 ± 0.2 MPa and an elongation at break of 487 ± 41 %. membranes prepared from virgin and recycle polymers in reported
studies and this work. The rPET@PDMS_1 shows higher oil flux than
any membrane prepared by electrospinning. The main advantage of the
3.5. Separation performance of the PDMS-functionalized rPET membrane
current study in comparison to the previous reports is the employment
of rPET for the fabrication of the membrane. The materials used in the
Encouraged by the excellent superoleophilic and underoil super-
previous studies were virgin polymers, which could lead to another
hydrophobic properties of the rPET@PDMS membranes, a series of oil-
environmental issue [42]. The usage of the rPET reduces the plastics
water separation experiments were performed by using the setup, as
consumption that could bring an indirect benefit to the environment.
shown in Fig. 8a and Video S5. An oil-water mixture was poured onto
Besides, the rPET has a lower price than the virgin plastics; this usage
the prewetted membranes, which had been fixed between two parts of a
could provide a remarkable cost reduction.
filter holder. The result showed that only oil could permeate through
The oil-water separation performance of the rPET@PDMS_1 mem-
the rPET@PDMS membrane with high flux while the water was kept
brane was further investigated using three kinds of oil: ethylene tetra-
above the membrane, and no obvious water remained in the collected
chloride (C2H2Cl4), carbon tetrachloride (CCl4) and bromobenzene
oil. The selective permeation of the nanofibrous membrane for oil and
(C6H5Br), as shown in Fig. 8c. The results revealed that there was not
water can be explained by the estimation of intrusion pressure (ΔPc )
much difference in terms of the separation performance of the rPET@
based the Young-Laplace theory and a simplified equation:
PDMS_1 membrane when the used oils were ethylene tetrachloride and
2γL 2γ cosθ carbon tetrachloride. The fluxes could reach nearly 20,000 L h−1 m-2,
ΔPc = =− L
r R while the separation efficiency could be high, approximately 98.5 %.
However, when the bromobenzene was used as a testing oil, the flux
where ΔPc is the liquid intrusion pressure, γL is the surface tension of oil significantly decreased to 11,067 ± 1230 L h−1 m-2. The use of bro-
or water in air, r is the curvature radius of meniscus, θ is the contact mobenzene caused the swelling of the PDMS layer on the membrane
angle of the liquid on the surface of fibers, R is the equivalent pore and reduced the pore size of the membrane, leading to a decrease in oil
radius of the membrane. When the oil contacts the surface of membrane flux.
in air, γO is the surface tension of oil, and θO is the contact angle of oil on Membrane fouling is a common and difficult issue during oily water
the surface of fibers, which is nearly 0° owing to the superhydrophilicity treatment in practical applications. An ideal membrane should possess
of the rPET@PDMS membranes. Consequently, the corresponding ΔPc both good antifouling properties and recyclability. Herein, the anti-
is < 0, which means that the surface cannot support a composite in- fouling performance against water was tested by detecting the oil flux
terface and will allow the oil to spontaneously permeate into the changes over numerous cycles using the rPET@PDMS_1 membrane. The
membrane with the capillary driving pressure of ΔPc . However, when membrane exhibited an outstanding performance with nearly no flux
the water contacts the surface of membrane, the water contact angle

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H.N. Doan, et al. Journal of Environmental Chemical Engineering 8 (2020) 103921

Fig. 8. (a) Photograph showing the oil-water separation experiment. (b) Flux and separation efficiency of the rPET@PDMS fibrous membranes obtained from various
PDMS concentrations (C2H2Cl4-water, 50 % v/v). (c) Flux and separation efficiency of different kinds of oil using the rPET@PDMS_1 membrane. (d) Changes in the
water flux with increasing separation cycles of the oil-water mixture using the rPET@PDMS_1 membrane. (e) Designed system for the continuous separation of a light
oil-water mixture.

decrease and kept a high separation efficiency of 98.5 % after ten cycles 4. Conclusion
due to its excellent water-repelling ability.
Besides, another advantage of the rPET@PDMS membrane com- A low-cost and environmentally friendly fibrous membrane for oil-
pared to other commercial adsorbents is that they can be used as se- water separation was successfully fabricated. The PDMS-functionalized
paration media for the continuous collection of light oil from an oil- rPET membranes with superoleophilic and underoil superhydrophobic
water mixture. As shown in Fig. 8e and Video S6, the rPET@PDMS_1 properties were made using electrospinning and dip-coating methods.
membrane was fixed to a membrane holder connected to a vacuum The morphology, chemical composition, thermal and mechanical
pump to yield a pressure-driven flow for oil-water separation. With properties, surface wettability and oil-water separation performance of
superoeleophilic properties, the oil can rapidly permeate through the the rPET membrane can be controlled by manipulating the PMDS
membrane. On the other hand, the underoil superhydrophobicity pre- concentration in the dip-coating solution. The rPET@PDMS membrane
vents the water from permeating through the membrane, leading to the shows a high oil-water separation performance with excellent anti-
high oil-water separation efficiency of the system. Because of its ex- water fouling behavior. Because of its outstanding anti-water fouling
cellent separation properties, the rPET@PDMS_1 membrane is able to properties, the rPET@PDMS membrane is able to keep a high separa-
separate different oil-water mixtures and thus has potential industrial tion performance after ten cycles, thus possessing great potential for oil-
applications. water separation procedures.

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H.N. Doan, et al. Journal of Environmental Chemical Engineering 8 (2020) 103921

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