Separation and Purification Technology 259 (2021) 118081

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Separation and Purification Technology

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

Facile fabrication of eco-friendly polycaprolactone (PCL)/Poly-D, L-Lactic

acid (PDLLA) modified melamine sorbent for oil-spill cleaning and water/
oil (W/O) emulsion separation
Vinothini Arunagiri a, Adhimoorthy Prasannan b, *, Jittrakorn Udomsin a, c, Juin-Yih Lai a, c, d,
Chih-Feng Wang a, c, Po-Da Hong b, Hsieh Chih Tsai a, c, *
a
Graduate Institute of Applied Science and Technology, National Taiwan University of Science and Technology, Taipei, Taiwan, ROC
b
Department of Materials Science and Engineering, National Taiwan University of Science and Technology, Taipei, Taiwan, ROC
c
Advanced Membrane Materials Center, National Taiwan University of Science and Technology, Taipei, Taiwan, ROC
d
R&D Center for Membrane Technology, Chung Yuan Christian University, Chungli, Taoyuan, 320, Taiwan, ROC

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

Keywords: Accidental crude oil spillages immensely impact the biological functions of living organisms in ocean waters such
Polycaprolactone (PCL) as respiration, feeding, and thermoregulation. Recent studies have highlighted compostable hydrophobic poly­
Poly-D meric oil sorbents as requisite resources for oil-spill cleaning, owing to the release of non-toxic degrading ele­
L-Lactic acid (PDLLA)
ments in the water. Hence, we investigated the applications in oil-spill cleaning of a modified commercially
Oil sorbents
Melamine
manufactured 3D porous melamine sponge obtained via dip-coating a pore-filling eco-friendly polymer com­
Separation posite (PCL/PDLLA), using an inexpensive freeze-drying technique. The FE-SEM morphology analysis of the PCL/
PDLLA fabricated melamine sorbent blend displayed an emergent interconnected porous structure, along with an
improved hydrophobicity of 162◦ (WCA) & 180◦ (UOWCA) with super-oleophilic wettability, as indicated by
water angle analysis. Furthermore, physicochemical interactions through Fourier Transform Infra-Red Spec­
troscopy (FT-IR), Raman mapping, X-Ray Diffraction (XRD), tensile test with 92% elongation were confirmed
between the melamine sponge and PCL/PDLLA composite. Our PCL/PDLLA modified melamine sorbent
exhibited oil absorption capacity ranges of 3.3~8.7 g/g to disparate viscous oils (n-hexane, n-octane, soybean oil,
crude oil, motor oil), while possessing a 99.99% oil purity with an approximate 560.737 Lm-2h− 1 flux for W/O
emulsion separation under gravity. In conclusion, we highlight the capabilities of eco-friendly PCL/PDLLA
(80:20) modified melamine as trade off in oil-spill cleaning sorbent along and oil separator from W/O emulsion,
with appropriate physicochemical stability and reusability.

1. Introduction Consequently, thick oil becomes catastrophic to marine wildlife such as

Worldwide, water is an essential use of living organisms and highly
demanded over the impact of the industrial revolution and advanced
science & technology [1,2]. However, water scarcity and water pollu­
tion that typically occurs in the oceans also increasing potentially [3].
Especially, anthropogenic ocean pollution occurs daily as oil spills (for
instance, a terrific explosion of British petroleum(BPs) deep water ho­
rizon oil rig release in the Gulf of Mexico in 2010), oil leaks, refining,
storage, handling, transportation, offshore drilling, routine maintenance
activities, road runoff, etc. [4–6]. Particularly, Oil spill displays vital
problem because of stagnant thick oil sludge on the seawater surface.
fish, birds, sea otters, and also hinder light for photosynthesis in marine
plants along-with escorting inevitable damage to the soil fertility and its
porosity [6,7].
There are four main conventional oil-spill cleaning methods:
Chemical (dispersants), Physical (burning), Biological (bioremediation),
and Mechanical (oil booms, skimmers, separators, sorbents) [8–14].
Sorbents constitute the primary conventional mechanical method for
passive oil removal, by possessing increased affinity to oil and following
both adsorption and absorption mechanisms [8,10,15]. The second most
efficient method for emulsified oil/water mixture separation is mem­
brane separation technology. Both methods are widely used owing to

* Corresponding authors at: Graduate Institute of Applied Science and Technology, National Taiwan University of Science and Technology, Taipei, Taiwan, ROC.
E-mail addresses: ak.prasannan@mail.ntust.edu.tw (A. Prasannan), h.c.tsai@mail.ntust.edu.tw (H.C. Tsai).

https://doi.org/10.1016/j.seppur.2020.118081
Received 9 September 2020; Received in revised form 7 November 2020; Accepted 13 November 2020
Available online 19 November 2020
1383-5866/© 2020 Elsevier B.V. All rights reserved.
V. Arunagiri et al.
their cost-effectiveness, eco-friendliness, simple orientation, and ease of
deployment [2,10,16].
Sorbents used in oil-spill cleaning vary in nature, ranging from nat­
ural inorganic and/or natural organic/polymeric materials as well as
agricultural products and synthetic adsorbents [17]. However, the
above stated sorbent materials present deficiencies such as lack of
porous 3D structure as well as decreased elasticity, flexibility, me­
chanical properties, oil-penetrating capacity, softness, surface area,
thermal stability, bulk density, and reusability. Thus, researchers have
shifted focus to tackling modern requirements by investigating 3D
porous commercial melamine sponges composed of formaldehyde mel­
amine sodium bisulfite-copolymer (C4H9N6NaO4S) to be widely utilized
as sorbents and membrane separators [9,11,17]. However, selective oil
absorption is hindered by the amphiphilic behavior of melamine
sponges. Hence, researchers focus on establishing hydrophobic mel­
amine sorbents as oil-spill cleaning agents. Some of the existed hydro­
phobic melamine sorbents were obtained by dip-coating hydrophobic
polymers, nanoparticles, silanes, and carbon materials via in situ
chemical vapor deposition (CVD), which however, release toxic pollut­
ants to the environment [18].
Contrarily, eco-friendly polymers release non-toxic elements during
degradation, thus, remaining non-pollutant to the environment while
providing with potential melamine sponge modifiers due to their ver­
satile sorbent nature. PCL and PLA are two primary synthetic hydro­
phobic candidates, possessing sorbent and separator behavior for oil-
spill cleaning, owing to their microporous matrix formation, excellent
biodegradability, and strong mechanical properties [19–24]. Nowadays,
biodegradable polymer blends own advantages in biomedical research
and industrial use owing to the ease of blending, cost-effective,
enhancing physical and mechanical properties of homo-polymers
[25,26]. Moreover, PCL/PDLLA blend is a recognized as supreme com­
posite by remunerating mutual weakness in mechanical strength and
physicochemical properties [27,28]. PCL is a slow degrading semi-
crystalline polyester exhibit low glass transition temperature (Tg)
(− 60 ~ − 50 ◦ C) along with low mechanical strength and high elonga­
tion rate. PDLLA is a fast degrading amorphous polymer formed via
polymerization of a racemic mixture of D and L lactic acid with rela­
tively high Tg (55–60 ◦ C) [19,29].
In our research, we investigated the effects of eco-friendly PCL/
PDLLA modified melamine sorbent on oil absorption and emulsified
oil–water separation. Initially, PCL was blended with PDLLA in 10 wt%
and at varying weight ratios (90:10, 85:15, 80:20) to obtain potent
hydrophobic polymer solutions. For every hydrophobic pore-filling
PCL/PDLLA blend ratio, melamine was used as a substrate and dipped
to achieve interconnected porous morphology via a facile freeze-drying
technique. A specific PCL/PDLLA melamine sorbent ratio (80:20)
exhibited high viscous oil absorption capacity (3.3–8.7 g/g) with
99.99% oil purity and flux of 560.737 L m-2h− 1 to water/oil emulsion
separation. Therefore, we highlighted that a facilely and innovatively
fabricated PCL/PDLLA melamine blend can act as a tradeoff and eco-
friendly in high-viscous oil sorbent and emulsified water/oil separator,
with sufficient physicochemical stability and reusability.
2. Experimental section
2.1. Materials
Unaltered polycaprolactone (PCL) average Mn ~ 10,000 and
1,4dioxane were purchased from Sigma-Aldrich. Poly (D, L-lactic acid)
IV 2.0 dl/g was obtained from Polysciences Inc company. Deionized
water for the experiment was collected from the Millipore Sigma water
purification system. The melamine sponge substrate was obtained from
BASF corporation company. The n-hexane oil used for the absorption
and emulsion separation experiment was obtained from Sigma Aldrich.
Additionally, soybean, motor, and crude oil used in absorption experi­
ments are commercially available products, while n-octane is obtained
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Separation and Purification Technology 259 (2021) 118081
from Alfa Aesar. Further, isooctane oil used in under oil-water contact
angle measurement were also obtained from Alfa Aesar.
2.2. Fabrication of PCL/PDLLA melamine sorbent via dip-coating freeze
dry method
PCL and PDLLA were blended in 1,4-dioxane solvent to 3 separate 10
wt% solutions with different weight ratios (90:10, 85:15, and 80:20).
Pristine Melamine Sponge (PM) was cut into 3 circular pieces (2 cm in
diameter), which were subsequently dipped in the above mentioned
blends. Following freezing at − 20 ◦ C and subsequent vacuum freeze-
drying for 24–48 h, we achieved an interconnected porous structure
we achieved an interconnected porous structure through removal of
frozen solvent crystals.
2.3. Physicochemical characteristics
Using scanning electron microscopy (SEM, JEOL JSM-6500) oper­
ating at a 20 kV accelerating voltage, we observed the surface mor­
phologies of PCL 10 wt%, PDLLA 10 wt%, and PCL/PDLLA 10 wt%
(90:10, 85:15, and 80:20 ratios) modified melamine sorbents. Polymer
blend interactions between melamine dipped PCL and PDLLA were
confirmed through attenuated total reflection infrared (ATR-IR) spec­
troscopy (Nicolet 6700, Thermo Scientific). The crystalline nature of
polymers were observed and confirmed through X-ray diffraction (XRD)
measurement by a Bruker D2 PHASER, which is operated with a light
source of rotating anode copper target wavelength of about 0.154060
nm, 18KW high voltage power supply, cathode tungsten filament: 0.5 ×
10 mm wire out of light and vacuum closed environment. The me­
chanical properties of the polymers were tested with the length of 0.3
mm at vertical orientation. Upon the polymer-coated melamine sponge
membrane 3 μL droplets of water were placed and the images were
obtained via contact angle analysis (Model 100SL, Sindatek Instrument
Co., Ltd., New Taipei, Taiwan). The oil content of the filtrate and feed for
all samples was quantified on a vario -total organic carbon (TOC)-ele­
mentar analyzer (Germany) and a C10S/coulometric KF titrator from
Mettler Toledo company was used accordingly for water content (results
are listed in Table 2). Feed and filtrate solution absorbance were
observed via ultraviolet–visible (UV–vis) spectrometry (Jasco V-970)
(Table 3).
2.4. Stability of the PCL/PDLLA melamine sorbents
The chemical and physical stability of the 1 cm × 1 cm × 1 cm
polymer-coated membrane sample were tested in varying harsh envi­
ronments, such as dipping in 3.5% NaCl ,1 M HCl aqueous solution, n-
hexane, ethanol and n-hexane/water emulsion for 24 h as well as 24 h
UV exposure. Additionally, harsh physical treatment of the sample was
conducted through rubbing with abrasive paper (220 grit size) at 80 m/s
for 3 min. Finally, we performed contact angle measurements with 3 μL
of water and oil, separately.
2.5. Oil absorption experiment in oil spill cleaning
Oil absorption experiments were performed by dipping PCL/PDLLA
melamine sorbents in 6 mL total volume of immiscible various viscous
oils (hexane, n-octane, soybean oil, motor oil, castor oil)/water mixtures
(1:1 vol ratio), for 15 min. The samples size was 1 cm × 1 cm × 1 cm
with an approximate weight of 0.05 ~ 0.1 g. The oil absorption exper­
iment was carried out for three individual samples, after calculating the
average weight for reference.
The absorption capacity of the melamine sorbent was calculated by
formula (1):
mt − mo
Q= (g/g) (1)
mt
V. Arunagiri et al.
where Q is the absorption capacity, mo is the weight of the membrane
before absorption, mt is the weight of the membrane after absorption.
2.6. Gravity driven surfactant stabilized W/O emulsion preparation and
separation
Stabilized water/oil emulsion was prepared by dissolving 0.08 g of
Span® 80 nonionic surfactant in 200 mL of oil (hexane), followed by
stirring. Then, 2 mL of water were added dropwise and stirring
continued for 3 h at 1000 rpm until a milky white solution was achieved.
Water/oil (W/O) emulsion separation was conducted through simple
gravity filtration with a fixed sample weight of 1.5 g at height of about
5.2 cm. Approximately 20 mL of stabilized (W/O) emulsion surfactant
was poured into the container and noted down permeation time of
emulsion. The oil purity and flux were calculated by formulas (2) and
(3):
water content in ppm
Oil purity% = 100 − (2)
10000
Q
J= Lm− 2 h− 1
(3)
AΔt
where J is the W/O emulsion permeation flux, Q is the volume of filtrate
collected in liters, A is the surface area (πr2) in m2, and Δt is the time
taken for filtration of the collected sample in hours.
2.7. Repeatability/reusability
The repeatability test was performed for 5 cycles. Each cycle was
proceeded with ethanol washing. Further, flux and oil purity were
calculated.
3. Results and discussion
3.1. Optimized PCL/PDLLA composition
Melamine modified sorbents such as hydrophobic polymers, nano­
particles, silanes, and carbon materials do not possess biodegradable
properties. Therefore, leaking toxic elements and gases to the environ­
ment, and deteriorating global warming. However, biodegradable
polymers constitute eco-friendly materials that can degrade non-toxic
elements while remaining non-pollutant to the environment. Hence,
we designed eco-friendly PCL/PDLLA polymer blend as a hydrophobic
coating on melamine sponge for W/O emulsion separation, and oil-spill
cleaning. Different compositions (5%, 7.5%, and 10%) of PCL/PDLLA
were blended with 1,4 dioxane solvent, followed by a freeze-drying
process, during which homogeneous honeycomb structures were
formed through the sublimation process of dioxane solvent ring struc­
ture [30]. Freeze-drying is a simple and easy technique that follows
three steps to form a porous cake. The first step involves in cooling of
liquid sample solution and formation of ice crystals (freezing). The
second step involves heating up of frozen samples at room temperature
and low pressure (sublimation of solvent crystals/primary drying). The
third step involves the desorption of unfrozen water substances remains
after sublimation (desorption of water /secondary drying). The freeze
drying technique also assisted in enhancing the chemical stability of the
materials during the drying process [31,32]. Accordingly, we observed
homogeneous porous morphology in every (5, 7.5, and 10 wt%)
composition of PCL, PDLLA, and PCL/PDLLA blends (Fig. 1a-i) [33].
Thermally induced phase separation (TIPS) with optimized temperature
parameters further enhanced porous morphology [34]. FT-IR spectros­
copy was used to observe the interactions in PCL/PDLLA blends (Fig. 1j).
The PCL 10% consists of C = O peaks around 1722 cm− 1 along with CH
stretching and bending peaks around 2944 cm− 1 and 2865 cm− 1. The
PDLLA 10% polymer exhibits C– – O peaks around 1745 cm− 1 with CH3
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Separation and Purification Technology 259 (2021) 118081
peak around 1375 cm− 1, and C–O–C ester peak around 1182 cm− 1.
Furthermore, in PCL/PDLLA blends, we observed CH stretching and
bending of PCL around 2944 cm− 1 and 2865 cm− 1, along with a slight
shift of Symmetric C–O–C bond stretching of PDLLA from 1178 cm− 1
to 1186 cm− 1 [35]. The above results corroborate the hydrogen bonding
interactions between the H bond of terminal CH3 chain of PDLLA, and O
terminal bond of PCL [36]. In addition, hydrogen bonding interaction
was confirmed through the broader OH peak shift from 3457 to 3392
cm− 1. Since our research goal was to utilize biodegradable polymer
solution in W/O separation. We investigated the surface wettability of
different compositions of PCL, PDLLA, and PCL/PDLLA blends [37].
The water contact angles in air for different compositions of PCL,
PDLLA, and PCL/PDLLA. We observed that as the percentage concen­
tration of PCL, PDLLA, and PCL/PDLLA composite increased, hydro­
phobicity further increased owing to the rough homogeneous
microporous surface and high percentage of polymer content. Thus, we
decided to use 10% PCL/PDLLA blends for further experiments Table 1.
3.2. Electron microscopy structural view of PCL/PDLLA melamine
sorbent
The pore size of pristine melamine sponge was estimated at 95–100
µm, therefore hindering nanosized W/O emulsion separation. Conse­
quently, we opted to develop interconnected microporous structure into
the melamine surface macroporous. In Section 3.1 we discussed how
PCL/PDLLA blend can form homogeneous micropore structure with
hydrophobic surface. Accordingly, we followed the dip-coating process
to cover the entire macroporous melamine surface with hydrophobic
polymer solution. Dip-coating is a widely used facile technique owing to
the merits of low cost and layer adjustment in sorbent to achieve hy­
drophobic surface, which results in selective oil absorption with suffi­
cient water repellency during the oil/water separation process. The four
forces mainly followed in dip coating process are force of inertia, viscous
drag, gravitational force and surface tension [38]. Further in dip coating
process, immersing melamine substrate into polymer solution results in
deposition of PCL/PDLLA material for effective porous formation via
freeze drying technique. Due to sublimation process of solvent evapo­
ration occurs during the freeze-drying process, an interconnected
microporous coverage of 3D skeleton surface was observed in different
ratios (90:10, 85:15, and 80:20) of PCL/PDLLA modified melamine
sorbents with pore size of about 24–30 µm, 20–30 µm, and 5–20 µm,
respectively (Fig. 2d, e, f). PCL 10%, and PDLLA 10% were unable to
cover the melamine sponge 3D skeleton and rough homogeneous
interconnected pore structures, depositing PCL polymers with pore size
of about 50 µm (Fig. 2b) and exhibiting porous formation in PDLLA 10%
melamine sorbents with pore size of about 36–48 µm (Fig. 2c). The PCL/
PDLLA (80:20) blend exhibited an interconnected microporous matrix
structure with a 5–20 µm pore size (Fig. 2f).
3.3. Physicochemical characteristic of PCL/PDLLA melamine sorbent
Interactions within the melamine PCL/PDLLA blend were confirmed
through FT-IR spectroscopy (Fig. 3a). The pristine melamine sponge
exhibited a triazine ring peak around 812 cm− 1. Furthermore, 1◦ and 2◦
N–H bending, C–N stretching, C–H bending, C–O stretching peak
were observed at 3370 cm− 1, 1734 cm− 1,1634 cm− 1, 1426 cm− 1, and
1216 cm− 1, respectively [39–42]. In PCL 10 wt%, PDLLA 10 wt%, and
10 wt% PCL/PDLLA (90:10, 85:15, and 80:20) melamine sorbents we
observed a primary amine peak at 3370 cm− 1 disappearing, along with
C–H bending peaks at 3018 cm− 1 and 2942 cm− 1. Further, C– – O ester,
C–O–C ester, and triazine ring peaks attributed at 1724 cm− 1, 1070
cm− 1, and 812 cm− 1, respectively. The process of dip-coating revealed
interactions between the primary amine group of pristine melamine, and
carbonyl groups of PCL/PDLLA blend [10,37,43]. Despite PCL possess­
ing low hydrophobicity, the aliphatic chains, ester group and porous
morphology in PDLLA stimulates increased hydrophobicity in PCL/
V. Arunagiri et al. Separation and Purification Technology 259 (2021) 118081

Fig. 1. FESEM images of a-c) PCL of 5,7.5 and 10 wt%, d-f) PDLLA of 5,7.5 and 10 wt%, and g-i) PCL/PDLLA (90:10) of 5, 7.5 and 10 wt%, respectively, and j) ATR-
FTIR of PCL, PDLLA and PCL/PDLLA (90:10) of 10 wt%

PDLLA (80:20) [35]. Generally, pristine melamine and PDLLA exist as

Table 1 amorphous compounds; however, during interaction with crystalline
Wettability of Different composition of PCL, PDLLA and PCL/PDLLA porous
PCL polymers, PCL/PDLLA melamine sorbent was confirmed through
substrate.
XRD spectroscopy to alter its crystallinity patterns, with PCL angled at
Material/Composition 5% 7.5% 10% 2θ = 21.3 and 23.6 (Fig. 3b) [27,44,45]. Considering the increased
PCL on silica substrate 67.7◦ 51.9 ◦ 90.0 ◦
elasticity and load–displacement curve of polymeric materials, we
PDLLA on silica substrate 63.4 ◦ 62.8 ◦ 73.4 ◦
PCL/PDLLA (90:10) on silica substrate 53.8 ◦ 73.8 ◦ 100 ◦ traced the force vs displacement graph while calculating elasticity and

4
V. Arunagiri et al.
Fig. 2. FE-SEM aerial view image of a) pristine melamine sponge, b) PCL 10 wt%, c) PDLLA 10 wt% melamine, d) 10 wt% PCL/PDLLA (90:10), e) 10 wt% PCL/
PDLLA (85:15), and f) 10 wt% PCL/PDLLA (80:20) melamine sorbent.
testing the tensile strength of PCL/PDLLA melamine sorbent (Fig. 3c).
Compared with pristine melamine, PCL/PDLLA (90:10,85:15, and
80:20) required higher amounts of force (10–16 N) for displacement to
occur at 1–3 mm, maintaining an elasticity of approximately 92–94%.
This is attributed to the reduced porosity and polymer stiffness of PCL/
PDLLA sorbents [29,46]. The mechanical properties of polymer blend
mainly controlled by the crystalline nature. Herein, variable mechanical
properties was observed in PCL/PDLLA blends owing to the impact of
crystalline PCL and amorphous PDLLA behavior. As semi-crystalline PCL
ratio becomes higher, the PCL/PDLLA (90:10) melamine modified
membrane exhibiting worse mechanical property owing to high brittle
behavior. Thus, resulted in lesser loading force obtained with shorter
displacement curve. Whereas, PCL/PDLLA (80:20) exhibits high plas­
ticity behavior by balancing amorphous nature of PDLLA and crystalline
behavior of PCL. Hence, results in higher loading of force for displace­
ment curve. Additionally, higher amount of amorphous PDLLA polymer
in PCL/PDLLA (80:20) gives a major contribution for better mechanical
properties. The hydrophobic rough surface was confirmed through
contact angle analysis (Fig. 3d). Considering that solid materials exhibit
higher surface energy and lower contact angles, increased hydropho­
bicity in 10 wt% PCL/PDLLA (90:10, 85:15, and 80:20) melamine blends
was observed at 151◦ ,158◦ , and 162◦ water contact angle (WCA) in air.
Whereas, under oil (Isooctane) water contact angle (UOWCA) of PCL/
PDDLA melamine blends (90:10,85:15, and 80:20) increase as 173◦ ,
175◦ , and 180◦ , while individual PCL and PDLLA melamine represent
155◦ and 163◦ , respectively. On increasing PDLLA ratio the porosity of
the sorbent increases and results in higher hydrophobicity. Contrarily,
dual wettability of oil/water was observed on the smooth, lower-energy
surface of pristine melamine [11]. The WCA and UOWCA for melamine
free PCL/PDLLA composite were observed and attached in supplemen­
tary [Fig. S3]. Furthermore, Raman peaks of PCL/PDLLA (80:20)
modifed melamine sorbent were identified from the color intensity of 3D
Raman mapping (Fig. 3g and Fig. 3h) upon focused dark spots (Fig. 3f)
while performing Raman mapping anaysis. The resultant peaks from the
dark spots were identified as 3400 cm− 1 (OH), 2942 cm− 1 (ʋCH), 1725
cm− 1 (ʋC– – O) cm− 1, 1437 cm− 1 , 1252 cm− 1 (ωCH), 1190 cm− 1 (δCH2),
and 976 cm− 1 (Triazine ring) [47,48]. Raman mapping analysis can
5
Separation and Purification Technology 259 (2021) 118081
provide strong evidence for PCL/PDLLA coating on the melamine
sponge through the analysis of polymer characteristic vibratons and
melamine sponge vibrational peaks. Thus, we preferred 2942 cm− 1
(ʋCH) vibrational peak for PCL/PDLLA peak, and 976 cm− 1 (triazine
ring) vibrational peak for melamine sponge to understand the depth of
polymer coating in melamine sponge through evaluation of 3D Raman
mapping (Fig. 3g and h). The green color indicates the polymer
component concentration due to presence of PCL/PDLLA and yellow
color attributes to triazine ring component from the melamine sponge.
As seen in Fig. 3g, green color intensity increased upon the Z axis in 3D
Raman mapping, which attributes to the thick polymer coating on
melamine sponge as the z direction increases, whereas yellow intensity
(triazine ring) become decreased with respect of Z directions. To un­
derstand the thickness of polymer coating upon melamine sponge, 10
layer of stacking lines image (Fig. 3h) from 3D Raman mapping was
evaluated. Thick coating of polymer clearly visualized from the 4th layer
to 10th layer of stacked image, whereas the first three-layer exhibit
dominant triazine ring (yellow). Thus, 3D raman mapping results
reveled as a useful advanced technique to understand the coating of
PCL/PDLLA on the melamine sponge.
3.4. PCL/PDLLA melamine act as sorbent in oil absorption experiment
and chemical stability
Generally, sorbents are materials with increased affinity to oil,
following both adsorption and absorption mechanisms. Absorption and
adsorption are both possible when bio-polymer sorbents interact with
oil, and subsequently, we performed absorption experiments for 15 min
in 1:1 oil/water volume ratio using disparate viscous oils (n-hexane, n-
octane, soybean oil, motor oil) and PCL 10 wt%, PDLLA 10 wt%, and
PCL/PDLLA 10 wt% (90:10, 85:15, and 80:20) melamine sorbents
(Fig. 4a, b, c). Absorption occurs in three steps: oil diffusion on the
surface, capillary action of entrapping oil, oil agglomerates on the rough
porous surface. In PCL/PDLLA melamine sorbents, the above steps are
completed within 30 s for high viscous motor oils. The oil absorption
capacities of PCL 10 wt% and PDLLA 10 wt% melamine sorbents were
found to be 2.5–5.5 g/g and 3.5–5 0.9 g/g respectively. Whereas PCL/
V. Arunagiri et al. Separation and Purification Technology 259 (2021) 118081

Fig. 3. a) FT-IR, b) XRD, c) tensile strength and d) water contact angle (WCA) and Under oil (Iso-octane) water contact angle (UOWCA), and Raman mapping
analysis of PCL/PDLLA (80:20) modified melamine sorbents e) Raman peaks, f) dark spots, g) 3D Raman mapping, and h) 3D stacking image.

PDLLA (90:10, 85:15, and 80:20) exhibited higher absorption capacity
at 3.3–4 0.3 g/g, 3.5 ~ 5.8 g/g, and 3.9–8.7 g/g, corresponding to each
ratio (Fig. 4d). Due to capillary movement into the pores of the sorbent
during absorption, low viscosity oils were trapped quicker into the inner
voids than higher viscosity oils. Further, high viscous oils were hard to
move out of the sorbent tend to remain as more oil in the sorbent
resulting in higher absorption capacity [17,49,50]. Thus, amongst var­
ied melamine sorbent ratios, PCL/PDLLA (80:20) exhibited higher
absorption capacity (3.9–8.7 g/g) in high viscosity oils. The saturation
point of motor oil absorption was calculated [Fig. S2]. Given the pre­
pared PCL/PDLLA melamine sorbent’s higher oil absorption capacity,
we focused our investigation to determine its chemical stability under
corrosive environment, considering it constitutes an important sup­
porting factor for practical applications in oil-spill accidents for long-
term use. Therefore, the as-prepared varied ratios (90:10, 85:15, and
80:20) of PCL/PDLLA melamine sorbent underwent dipping in 1 M HCL

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and 3.5% NaCl aqueous solution, ethanol, n-hexane, n-hexane/water
emulsion, UV exposure for 24 h, and abrasion test. Furthermore, water
contact angles (WCA) in air of the above sample were observed via
contact angle analysis (Fig. 4e) [Fig. S4]. The PCL/PDLLA melamine
sorbent showed stability and exhibited a reasonably slight decrease in
water contact angle ranging from 96.5 to 153◦ under a harsh environ­
ment. Compared with other ratios, PCL/PDLLA (80:20) can be utilized
as an excellent sorbent for oil-spill cleaning and oil–water separation
even under a corrosive environment, since the hydrophobicity of the
membrane was maintained at 136–153◦ except in abrasive test exhibited
100◦ [51].
3.5. PCL/PDLLA melamine act as membrane in gravity driven water in oil
emulsion separation
Miscible emulsions like oil-in-water/water-in-oil are generally diffi­
cult to separate, excluding when hydrophobic melamine sponges/eco-
friendly polymer sorbents are utilized. Therefore, we carried out W/O
(n-hexane) emulsion separation in 10 wt% PCL/PDLLA (90:10, 85:15,
and 80:20 ratios) melamine sorbent via conical filtration device
(Fig. 5a). The W/O (n-hexane) emulsions were prepared by using Span®
80 surfactants, presenting milky white color (Fig. 5c). Subsequently, the
PCL/PDLLA modified melamine sorbents were utilized to obtain sepa­
rate transparent oil (n-hexane) filtrate from span® 80 stabilized W/O (n-
hexane) emulsion (Fig. 5d). Water droplets for feed and filtrate were
viewed through optical microscopy. Compared with the milky white
Fig. 4. Oil absorption image of PCL/PDLLA (80:20) melamine sorbent a) hexane in water, b) motor oil in water, c) crude oil in water, d) absorption capacity, e)
chemical stability of PCL 10 wt%, PDLLA 10 wt%, and PCL/PDLLA 10 wt% (90:10, 85:15, and 80:20) melamine sorbents during 24 h exposure in 1 M HCL, 3.5% Na
Cl, UV light, abrasion test, polar ethanol solvent, non-polar hexane solvent and n-hexane/water emulsion dipping.
7
Separation and Purification Technology 259 (2021) 118081
feed used in separation (Fig. 5c), the collected filtrate presented absolute
transparency without a single droplet of water (Fig. 5d). Permeation
fluxes and oil purity were calculated for each sorbent (Fig. 5b). In the
cases of PCL 10% and PDLLA 10%, the oil purity was measured at
99.98%, whereas the varying ratios (90:10, 85:15, and 80:20) of PCL/
PDLLA coated melamine membranes, exhibited 99.99%, 99.99%, and
99.99%, respectively. The separation flux of PCL 10% was not higher
than other PCL/PDLLA modified sorbents (85:15 and 80:20). This is due
to the crystalline nature of PCL, which possess larger pore size with
smoother surface, whereas PDLLA 10% exhibited higher flux of about >
1800 L m-2h− 1 than all other PCL/PDLLA modified melamine sorbent.
This is attributed to the elevated humidity results of the highly rough
porous surface from the amorphous nature polymer backbone, which
can be enhanced the oil permeation flux due to it lose polymer chain
packing [22,52]. The separation flux for the three different ratios of
PCL/PDLLA 90:10, 85:15, and 80:20 were measured at 380 L m-2h− 1,
450 L m-2h− 1, and 560 L m-2h− 1 respectively. Therefore, among the
three ratios, PCL/PDLLA (80:20) acts as an advantageous separator for
water-in-oil emulsions, with a 99.99% oil purity with high permeation
flux [Fig. S5]. Additionally, we like to give a hypothetical conclusion
that PCL/PDLLA melamine membrane have capability to separate some
other complex emulsion oils like crude oil, motor oil, etc. Therefore, we
highlight that our prepared PCL/PDLLA melamine can act as both sor­
bent and membrane in oil spill cleaning and W/O emulsion separation,
respectively.
The higher oil content in filtrate than feed arise owing to pre-wetting
V. Arunagiri et al. Separation and Purification Technology 259 (2021) 118081

Fig. 5. a) Emulsion filtration set up b) Oil (n-hexane) purity and permeation flux, optical microscope of c) feed, and d) filtrate.

of membrane with n-hexane oil. Amongst the three ratios, PCL/PDLLA

(80:20) melamine sponge exhibited the lowest water content at 37 ppm,
due to the increased separation efficiency of the membrane (46245 ppm
of oil content in filtrate) Table 2.

3.6. Repeatability/reusability test in PCL/PDLLA (80:20) melamine

sorbent

The PCL/PDLLA (80:20) melamine sorbent presented a significant

WCA (162◦ ), UOWCA (180◦ ), oil absorption (3.3 ~ 8.7 g/g), crystal­
linity, physicochemical stability, and high oil purity (99.99%), hence, it
incurred a repeatability test under gravity using water-in-oil (n-hexane)
emulsion. Through 5 cycles of repeatability, PCL/PDLLA (80:20) mel­
amine displayed 99.99–99.93% oil purity accompanied with slight
variation in permeation flux of 480–611 Lm-2h− 1. The fluctuated flux
(Fig. 6) occurs based on amount of oil blockage in pore and ethanol
Fig. 6. Oil purity and permeation flux in different cycles of PCL/PDLLA (80:20)
washing of membrane. Considering the abovementioned results, we
Melamine sorbent
firmly believe that PCL/PDLLA (80:20) can act as an environmentally-
friendly reusable emulsified oil separator.
sorbent, enhancing its oil wettability. Among the disparate ratios of
3.7. Wettability performance in PCL/PDLLA (80:20) melamine sorbent PCL/PDLLA (90:20, 85:15, and 80:20), PCL/PDLLA (80:20) exhibited
significant oil absorption and emulsified oil rejection properties, with
The commercially available pristine melamine sponges used in our sufficient physicochemical stability and reusability. Hence, we per­
experiment exhibited dual wettability of oil and water. Thus, via our formed further wettability tests on PCL/PDLLA (80:20) melamine sor­
dip-coating process followed by a freeze-drying technique, we modified bents and compared the results with pristine melamine sponges; aside
them into hydrophobic melamine sponges with selective oil absorption from primarily comparing their surface. Prior to coating, pristine mel­
properties, for oil-spill cleaning. The dip-coating process induced the amine presented a smooth white surface (Fig. 7a), whereas a rough
interconnected hydrophobic porous surface on PCL/PDLLA melamine hydrophobic white surface was observed in PCL/PDLLA (80:20) coated
melamine (Fig. 7b). Dual wettability was examined by applying dispa­
rate viscous oils (n-hexane, n-octane, soybean oil, petroleum ether,
Table 2
Oil (n-hexane) and water content in feed and filtrate.
motor oil, crude oil) and water droplets on pristine melamine (Fig. 7c),
where we observed selective oil absorption via spreading of oils on PCL/
Content PCL 10% PDLLA 10% PCL/PDLLA W/O Feed
PDLLA (80:20) melamine sorbent surface, with simultaneous hydro­
Oil (TOC) in ppm 45,065 46,719 47,319 (90:10) 43,191 phobic water droplets repulsion (Fig. 7d). Furthermore, water absorp­
38,025 (85:15)
tion in pristine melamine sponge (Fig. 7e) and repulsion of water in
46,245 (80:20)
Water in ppm 185 200 69 (90:10) 7758
PCL/PDLLA (80:20) melamine sorbent (Fig. 7f) were observed after
68 (85:15) dropping water on their surface. Further details pertaining to the
37 (80:20) wettability test are attached in supplementary data [Fig. S3].

8
V. Arunagiri et al. Separation and Purification Technology 259 (2021) 118081

Fig. 7. a) Pristine melamine (PM), b) PCL/PDLLA (80:20) melamine sorbent, oil and water absorption of c) pristine melamine and d) PCL/PDLLA (80:20) (blue-
water, red-hexane, maroon-octane, dark yellow-soybean oil, light yellow-motor oil, green-petroleum ether, and black crude oil). Water absorption of e) pristine
melamine and d) PCL/PDLLA (80:20).

4. Conclusion melamine sponge. Despite the variety of existing hydrophobic melamine

The consequences of thick oil spills upon ocean water surface
generate severe problems to living organisms. Thus, membrane science
technology and particularly melamine sponges are used predominantly
to clean oil spills and separate emulsified oil/water. The unique
amphiphilic behavior of melamine sponges, however, limits them to
selective oil absorption, motivating us to develop a hydrophobic
sorbents, they act as pollutants by leaking toxic element in the envi­
ronment. The hindrance encourages researchers to develop biodegrad­
able hydrophobic melamine sorbents for oil-spill cleaning. In this study,
our major goal was to develop eco-friendly PCL/PDLLA melamine sor­
bent through a dip-coating process followed by a facile freeze-drying
technique. We prepared disparate ratios (90:10, 85:15, and 80:20) of
interconnected porous PCL/PDLLA melamine sorbents for application in

Table 3
Comparison of oil absorption and emulsion separation to different modified hydrophobic melamine sorbents.
Hydrophobic Fabrication Method WCA (◦ ) Oil Absorption Emulsion Separation Ref.
Materials
Types of oils Absorption Feed Flux (L m- Eff. (%)
2 − 1
Capacity (g/g) h )

PCL/beeswax Electro-spun 153 Petrol, diesel, kerosene, gingelly oil, 16.95–31.05 g/ – – – [37]
nanofibrous sunflower oil g
Porous PLA film Phase Separation 153 Hexane, diesel, gasoline, Vegetable oil, 5 g/g – – – [53]
Petroleum ether
GO/MS Dip coating 162 CHCl3, DMF, hexane, acetone, ethanol, 160 wt/wt % – – – [54]
methanol, pump oil, soybean oil,
motor oil
USTC-6@GO@ Dip coating 130 Diesel oil, soybean oil, gasoline, 1200- 4300 wt – – – [55]
MS petroleum, n-hexane, bromo-benzene, %
DMF, THF, acetone, CCl4,
methylbenzene
MIL-DDT@MF In situ growth 151.8 Diesel oil, choloroform, DCM, n- 54.1–120.2 g/g – – – [56]
heptane, DMF, cyclohexane, PMS,
petroleum, toluene, cyclohexanone,n-
dodecane
Zr/MS One step solution immersion 130 DMF, tetrachloromethane, paraffin 70–181 g/g – – – [57]
liquid, chloroform, toluene,
cyclohexane, acetone, nhexane, ethyl
alcohol and soybean oil
PDVB- one-step 153 n-hexane, DMF, acetone, chloroform, 8–16.45 g/g – – – [58]
PDMS@MS impregnationecuring method soybean oil, toluene
BCM Immersing-adsorption- 155 n-hexane, dodecane, toluene, 201 g/g – – – [59]
pyrolysis method sunflower oil, DCM, styrene,
chloroform, pet, gasoline, hexadecane
PB/MS dipping–squeezing–curing 137.8to DCM, choloroform, acetone, Toluene, 117–140 g/g – – – [60]
process 144.5 ethanol, cyclohexane, DMF, ethyl
acetate.
PCL/PDLLA/ Dip-coating/Freeze-drying 162 n-hexane, n-octane, soybean oil, crude 3.3–8.8 g/g W/O and 560 99.99 This
MS technique oil, and motor oil W/O (5 560–611 99.99–99.93 work
cycles
repeat)

Abbreviation: PCL-Polycaprolactone, PLA-Poly-lactic acid, GO-Graphene Oxide, MS-Melamine Sponge, USTC-6-University of Science and Technology of China-6, MIL/
DDT- MIL53/1-dodecanethiol (DDT), zr-Zirconim, PB-Polybenzoxazine, BCM- biomass-decorated carbonaceous melamine, PVDB- Polydivinylbenzene, PDMS- poly­
dimethylsiloxane, PDLLA-Poly-D, L-Lactic acid, DCM-dichloromethane, DMF-dimethyl formamide, CCl4-Carbon tetrachloride, THF-tetrahydrofuran.

9
V. Arunagiri et al.
oil absorption and water-in-oil emulsion separation. From the above
ratios, PCL/PDLLA (80:20) exhibited significant oil absorption capacity
(3.3 ~ 8.7 g/g) and oil purity (99.99%), along with an emulsified oil
separation flux of 560.737 L m-2h− 1. Hereby, we synthesized a novel
eco-friendly PCL/PDLLA (80:20) melamine sorbent that can act as
tradeoff sorbent in oil-spill cleaning and emulsified oil separator, while
possessing sufficient physicochemical stability and reusability Table 3.
CRediT authorship contribution statement
Vinothini Arunagiri: Conceptualization, Methodology, Investiga­
tion, Writing - original draft. Adhimoorthy Prasannan: Validation,
Writing - review & editing, Formal analysis. Jittrakorn Udomsin:
Investigation, Formal analysis. Juin-Yih Lai: Resources, Funding
acquisition, Supervision. Chih-Feng Wang: Resources, Formal analysis.
Po-Da Hong: Resources, Formal analysis. Hsieh Chih Tsai: Resources,
Supervision, Conceptualization, Writing - review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
The authors would like to thank the Ministry of Science and Tech­
nology, Taiwan, (MOST 105-2221-E-011-133-MY3 and 105-E-2221-
011-151-MY3) for providing financial support.
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.seppur.2020.118081.
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