Advanced Membranes 4 (2024) 100080

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Advanced Membranes
journal homepage: www.keaipublishing.com/en/journals/advanced-membranes

Spray-assisted assembly of thin-film composite membranes in one process

Shiliang Lin a, Yanqiu Zhang b, Lu Shao b, Cher Hon Lau a, *
a
School of Engineering, University of Edinburgh, Robert Stevenson Road, EH9 3FK, UK
b
MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, State Key Laboratory of Urban Water Resource and Environment, School
of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin, 150001, PR China

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

Keywords: Spray coating has been exploited to fabricate and tailor the morphologies of various components in thin film
Thin-film composite membrane composite membranes separately. For the first time, here we exploit this technology to construct and assemble
Spray coating both the selective layer and porous support of a thin-film composite membrane in a single process. In our
Desalination
approach, spray-assisted non-solvent induced phase inversion and interfacial polymerization reduced the time
required to fabricate thin-film composite membranes from 3 – 4 days to 1 day and 40 min. Our approach did not
sacrifice membrane separation performances during desalination of a mixture comprising 2000 ppm of NaCl in
water at 4 bar and room temperature. At these conditions, compared to traditional thin film composite mem-
branes, the water permeance of our spray coated membranes was higher by 35.7 %, reaching 2.32 L m
2 h
1
bar
1, while achieving a NaCl rejection rate of 94.7 %. This demonstrated the feasibility of fabricating thin film
composites via spray coating in a single process, potentially reducing fabrication time during scale-up production.

1. Introduction layer is mainly used to provide mechanical stability to the membrane

without impeding water permeance [11].
Water scarcity affects over one-third of the global population [1,2], To construct a TFC desalination membrane, polyethersulfone (PES) is
and measures implemented to alleviate the stress on our current water commonly used for the porous support due to its high chemical resis-
supply mostly focus on improving the reuse rate of existing water re- tance, mechanical strength and heat stability [12]. Meanwhile, selective
sources [3,4]. This is because more than 97 % of water on Earth is layers of such membranes mostly comprise polyamide fabricated from
seawater [2,5], which is not suitable for human consumption or utiliza- the interfacial polymerization of diamines dissolved in water and acyl
tion in industry. This limitation can be resolved if salts in seawater are chlorides dissolved in organic solvents [13]. In industry, this is typically
separated from each other to produce clean, freshwater i.e., desalination achieved through dip-coating where a porous support layer is first dipped
[6]. To date, desalination can be achieved via distillation, electrodialysis into a water solution comprising the diamine. Excess diamine is removed
and membrane separations [7]. from the surface of the porous support prior dipping it into an acyl
Amongst these desalination technologies, membrane separations are chloride-organic solution [14]. Reactions between the diamine and acyl
considered as the most efficient and can reduce electricity consumption chloride via interfacial polymerization yield a dense polyamide layer on
by 78 % when compared to distillation [8]. Since the 1950s, reverse top of a porous support. In practice, it may take up to four days to
osmosis membranes have been widely used for desalination. However, fabricate a TFC membrane (Scheme 1) [15].
despite technological advances in reverse osmosis membranes, there The limitation of traditional TFC fabrication method is that the sur-
remains a trade-off between water permeance vs. salt rejection [9]. A face of porous supports cannot dissipate the reaction heat released by
potential solution for resolving this long-standing issue is developing thin exothermic interfacial polymerization reactions in a rapid and uniform
film composite (TFC) membranes that comprise a thin, dense selective manner, leading to the formation of crumpled and thick selective layers
layer deposited on a porous support layer. Thin selective layers are that reduce permeability and selectivity [16]. This can be resolved with
required to reduce resistance for mass transport of solvent molecules substrate-free interface polymerization where free-standing, highly
across the polymer film whilst providing a barrier to prevent the trans- crosslinked, 6-nm thin nanofilms with a water permeance of 2.7 L m
2
port of dissolved salt molecules [10]. Meanwhile the porous support h
1 bar
1 has been produced [17]. However, such films are difficult to

* Corresponding author.
E-mail address: cherhon.lau@ed.ac.uk (C.H. Lau).

https://doi.org/10.1016/j.advmem.2023.100080
Received 23 November 2023; Received in revised form 12 December 2023; Accepted 13 December 2023
Available online 18 December 2023
2772-8234/© 2023 The Authors. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co. Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
S. Lin et al. Advanced Membranes 4 (2024) 100080

Scheme 1. (a) Timeline comparison between a typical process and our all-in-one spray coating technique developed in this work to fabricate thin film composite
membranes. Details for fabricating b) porous support and c) selective layer using spray-assisted non-solvent induced phase inversion and interfacial polymerization,
respectively..

handle and transfer. This limitation can be overcome by depositing a added layer can cover the defects in the previous layers [26].
polydopamine layer on to the surface of the porous support prior poly- To date, spray coating has been used to fabricate crosslinked poly-
amide deposition and vacuum treatment [18]. The polydopamine layer dimethylsiloxane TFC membranes for ethanol/water separation [27],
functions as an adhesive that ensures robust attachment of polyamide fluorinated SiO2 TFC membranes for water/oil emulsion separation [28],
nanofilm on the porous support. Apart from substrate-free interfacial carbon nanotube interlayers that enhance the separation performances of
polymerization, TFC membranes can also be fabricated via molecular a polyamide TFC membrane [29], and polyamide-based TFC membranes
layer-by-layer (mLbL) assembly. This technique requires alternate im- via a hybrid blade coating-spraying-interfacial polymerization process
mersion of a porous support into separate toluene-based solutions con- [30]. We recently also deployed spray coating to fabricate the porous
taining diamines and acyl chloride until the desired number of mLbL support and using benign, bio-based solvents such as Cyrene™ [31], and
deposition cycle is reached [19]. The water permeance of such mem- using 2-methyltetrahydrofuran (2-MeTHF) and cyclopentyl methyl ether
branes was 1.48 L m
2 h
1 bar
1, 2.5-fold higher than those fabricated (CPME) to fabricate selective layers of TFC membranes [32]. The sepa-
via dip coating, while NaCl rejection rates reached 98.2 % [20]. Despite ration performances of TFC membranes fabricated from spray-assisted
enabling precise control over polyamide film thickness and roughness, techniques typically surpass those produced from traditional dip
questions remain about the suitability of these fabrication techniques for coating methods. This demonstrates the potential of fabricating high
scale-up production of TFC membranes. This is due to difficulty in performance TFC membranes using a well-established industrial tech-
handling brittle nanofilms and the complexity of mLbL procedures. nique and common chemicals.
Spray-assisted fabrication techniques such as electrospraying [21], Clearly, spray-assisted techniques are used to fabricate a single
and spray coating [22,23] offer control over polymerization reaction component of a TFC membrane. This means that spray coating is usually
kinetics and chemistry, membrane morphology and simplicity in mate- deployed to produce either the porous support before dip coating or the
rial handling. For example, in electrospraying, an electric field is used to selective layer on a pre-fabricated porous support layer. Such combina-
distribute amine-water and acyl chloride-hexane droplets, and evaporate tions do not streamline the TFC membrane fabrication process. To date,
the solvents, to form a polyamide selective layer on a porous support spray coating has not been deployed to fabricate both the porous support
layer. Such TFC membranes present a reasonable NaCl rejection of 94 % and selective layers in a single process. Here we hypothesize that this
and a water permeance of 14.7 L m
2 h
1 bar
1 [21]. Such membranes knowledge gap can be addressed by enabling both non-solvent induced
can take up to 120 min to fabricate [24], consuming significant energy phase separation (NIPS) and interfacial polymerization in a single pro-
during fabrication. Different from electrospraying, spray coating enables cess via automated spray coating. In this work, we validated this hy-
sequential deposition of reactant solutions on to the substrate. This af- pothesis using an automated spray coater developed in our previous
fords better control over the reaction behavior, whilst reducing fabrica- works to 1) deposit a PES-Cyrene™ dope solution, 2) enable spray-
tion time even during large-scale production [23]. Spraying allows assisted non-solvent induced phased inversion to fabricate a PES
reliable buildup of homogenous, multi-layered films whilst regulating porous support, and 3) drive the interfacial polymerization of trimesoyl
their thickness and roughness in conditions that are not achievable with chloride and m-phenylene diamine on the PES support to fabricate
dip coating [25]. As such, spray coating is widely used in industry to polyamide-based TFC membranes for desalination (Scheme 1). By
deposit polymer coatings to yield defect-free thin films as each newly delivering these mandatory steps for TFC fabrication in a single process,

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S. Lin et al. Advanced Membranes 4 (2024) 100080

we reduce membrane fabrication duration from 4 days to 1 day and 40 2.4. Spray-assisted fabrication of polyamide-PES TFC membrane
min, without affecting membrane separation performances during
desalination. Due to the neurotoxicity of n-hexane and health and safety reasons
[38,39], we did not use the spray-assisted technique to fabricate TFC
2. Experimental membranes using n-hexane. Instead, we used spray coating to deposit
CPME solutions containing trimesoyl chloride. 2 wt% of MPD was dis-
2.1. Materials solved in water to form the water phase solution, and 3 wt% TMC was
dissolved in CPME to form the organic phase solution. As shown in our
Polyethersulfone (E3020P) was kindly provided by BASF, Germany. previous work, a higher concentration of TMC is required to form dense
Cyrene™ was purchased from Circa Group Ltd, Parkville, Australia. polyamide selective layers when CPME is deployed as a solvent [32]. This
Cyclopentyl methyl ether (CPME), Polyvinylpyrrolidone (PVP, K30) and is attributed to the slightly enhanced water miscibility of CPME affecting
m-phenylenediamine (MPD, >99.5 %) were purchased from Sigma MPD diffusion behavior in the CPME-water interface [40–42].
Aldrich. Trimesoyl chloride (TMC, 98þ %) was purchased from Alfa The MPD-water and TMC-CPME solutions were loaded into the
Aesar. n-hexane and ethanol (EtOH, 99.99 % purity) were from Fisher reservoir of two separate spray guns with 0.2 mm nozzles, respectively.
Chemicals. Without changing the spraying pressure (4 bar) and spraying path, the
An automated spray-coating machine adapted from a commercial 3D- MPD-water solution was first deposited on top of the PES support (30 s).
printer was used here to fabricate the porous support and selective layers. Subsequently the TMC-CPME solution was deposited on top of the thin
Details of this machine can be found in our previous work [31]. A Harder layer of MPD-water solution (30 s) and allowed to rest for 30 s. This 30-s
& Steenbeck Evolution CRplus Action Airbrush with 0.6 and 0.2 mm rest period is required to allow interfacial polymerization to take place
nozzle set was purchased from Everything Airbrush, UK. A Creator Pro and form a polyamide thin film. These steps constitute to one spray cycle
3D printer was purchased from FlashForge, China. Servo motors, an that lasted for 90 s (60 s of spraying and 30 s of rest time). This cycle was
Arduino Uno R3 board and connecting cables were purchased from RS repeated for up to 5 times. Thereafter, the entire glass plate was placed
Components Ltd, UK. inside a 50  C oven for 5 min to allow the interfacial polymerization to
complete. The resultant TFC membranes were then stored in a deionized
water bath prior to further characterization. Depending on the number of
2.2. Fabricating PES porous supports via spray coating spray cycles, here we named these spray-coated membranes as
Polyamide-PES TFC (spray coating - 1 cycle) to Polyamide-PES TFC
PES dope solutions were prepared by dissolving 15 wt% PES and 1 wt (spray coating - 5 cycles).
% PVP i.e., porogen in Cyrene™ at 80  C. This dope solution was stirred
magnetically until complete PES dissolution, forming a viscous and 2.5. Membrane characterizations
transparent solution. This process took place over 24 h to ensure full
dissolution of the PES [33–37]. This dope solution was loaded into the The skin layer and cross-section morphologies of membrane samples
solution reservoir of a spray gun with a 0.6 mm nozzle set installed in- studied here were observed with a Carl Zeiss SIGMA HD VP Field
side. Spraying distance was set to 20 cm above a glass plate (15 cm  23 Emission Scanning Electron Microscopy (FE-SEM). All samples were
cm) placed on the build plate of the 3D printer. Building plate was set at dried for 12 h in a vacuum oven before SEM analysis. For cross-section
20  C throughout spray coating. 4 bar of nitrogen was supplied to the SEM characterization, membrane samples were first freeze-fractured in
spray gun and spray gun movement was controlled by the control circuit liquid nitrogen. A 10 nm-thin layer of gold was sputter-coated on to the
and stepper motors [31]. The spray gun moved across the glass plate to samples before imaging. An accelerating voltage of 5 kV was used to
ensure full coverage of the printing area. This process was repeated for 6 obtain SEM micrographs.
times at room temperature to produce a PES-Cyrene™ wet film with Fourier transform infrared spectroscopy (FTIR) was performed in
thickness around 200 μm. After the dope solution was deposited on top of attenuated total reflectance (ATR) mode on a Nicolet™ iS™ 20 FTIR
a glass plate, deionized water was deposited over 5 cycles on to the wet Spectrometer (Thermo Scientific™) with a Smart iTX™ diamond acces-
PES-Cyrene™ film via spray coating using 4 bars of nitrogen. The PES sory to characterize functional groups over a range of 500–4000 cm
1.
film was allowed to rest for 10 min for solvent exchange between water XPS Analysis was performed using a Kratos Axis SUPRA XPS fitted with a
and Cyrene™ to take place. Excessive water on the surface of the coag- monochromated Al kα X-ray source (1486.7 eV), a spherical sector
ulated PES membrane was drained away. The resultant PES membrane analyzer and 3 multichannel resistive plate, 128 channel delay line de-
was then used as a porous support for TFCmembranes. tectors. All data was recorded at 150 W and a spot size of 700 μm  300
μm. Survey scans were recorded at a pass energy of 160 eV, and high-
resolution scans recorded at a pass energy of 20 eV. Electronic charge
2.3. Conventional fabrication of polyamide selective layers neutralization was achieved using a magnetic immersion lens. Filament
current ¼ 0.27 amp, charge balance ¼ 3.3 Volts, filament bias ¼ 3.8
2 wt% of MPD was dissolved in water to form the water phase solu- Volts. All sample data was recorded at a pressure below 10
8 Torr and at
tion and 0.2 wt% of TMC was dissolved in n-hexane to form the organic 150 K temperature. Data was analyzed using CasaXPS v2.3.20PR1.0 and
phase solution. A PES porous support fabricated from the method out- the spectra were calibrated with C1s peak at 284.8 eV. Each PA sample's
lined in Section 2.2 was taped to a glass plate, with the top surface facing Atom% was calculated using the CasaXPS software and the crosslinking
upwards. This porous support was placed in the MPD-water solution for degree in each type of polyamide was calculated using the following
5 min. The amine-loaded PES support was removed from the solution and equations:
pressed with a roller to remove excessive amine solution, prior immer-
sion in the TMC-n-hexane solution. After 5 min of immersion in organic O 3m þ 4n
¼ (1)
solution, the TFC membrane was placed in a 50  C oven for 5 min to N 3m þ 2n
allow the interfacial polymerization to complete and washed with n-
hexane and water to remove unreacted monomers. This polyamide TFC mþn ¼ 1 (2)
was used for control experiments that yielded data required for bench-
m
marking the separation performances of other membranes developed in Crosslinking degree ¼ (3)
this work. As such, we named this membrane, Polyamide-PES TFC (dip mþn
coating).

3
S. Lin et al. Advanced Membranes 4 (2024) 100080

where O/N is the Oxygen and Nitrogen atomic ratio of polyamides, m When compared to PES support layers that coagulated in a water bath
and n are the portion of crosslinked and linear parts. All samples were (conventional method), the surface of our spray-assisted PES porous
dried for 12 h in a vacuum oven before analysis. AFM topography images support layer reported here was more porous (Fig. 1a and b). This in-
of the PES support and polyamide TFC membranes were obtained using a crease in surface porosity due to spray coating was also observed else-
Nanoscope IIIa Multimode scanning probe microscope (Bruker AXS Inc) where where spray-coated water droplets enabled a more instantaneous/
with an E-scanner in tapping mode using silicon cantilevers. No other faster inversion process that leads to the formation of more porous
image processing was applied except flattening, which was performed membranes [45]. We also observed that phase inversion achieved
here using Gwyddion. through spray-coated water droplets also led to the formation of mem-
branes with a sponge-like structure at the bottom side and shorter
2.6. TFC membranes desalination test finger-like pores at the top cross-section, when compared to membranes
produced via a phase inversion process over water immersion. This was
The water permeances of the PES and TFC membranes were measured similar to observations reported elsewhere [46]. The surface and
using triplicate samples and a Sterlitech stainless steel HP4750 stirred cross-sectional morphologies of PES membranes that were fabricated
dead-end cell. The feed solution comprised deionized water obtained with three to five spray-assisted water deposition were similar (Fig. S1).
from a lab-based water purification system and pressurized with nitrogen This indicated that NIPS process was completed after three water depo-
gas at 1 bar at room temperature to reach steady flow rate, then measured sition cycles. Meanwhile additional water deposition cycles were
at 3 bars. During filtration, the feed solution was stirred at 400 rpm. required for complete removal of residue Cyrene™. The pure water
Permeate samples were collected in capped flasks as a function of time, permeance of PES support layers fabricated via spray-assisted NIPS was
weighed, and analyzed. The permeance was calculated using the 135.65 L m
2 h
1 bar
1, 2-fold higher than PES support layers fabricated
following equation: using Cyrene™ and water immersion [31].

V
Permeance ¼ (4) 3.2. Chemical structure of TFC membranes as a function of spray cycles
AtΔP

where permeance (Lm
2 h
1 bar
1) is expressed in terms of V, the Here in this work, we deposited the selective polyamide layer on to
volume of the solvent passing through the membrane (L), A – effective the surface of the PES support layer via two methods – the traditional
membrane area (m2), t – operation time (h), and ΔP – the applied pres- approach of dip coating, and our technique of spray-assisted interfacial
sure (bar). polymerization using an automated spray coating machine. Regardless of
The salt rejection rates of TFC membranes were determined using a approach used, the deposition of selective layer took place in less than 20
2000 ppm NaCl water solution as feed solution and stirred at 400 rpm to min. ATR-FTIR was performed to determine the chemical composition of
avoid concentration polarization. The feed solution was pressurized at 3 all TFC membranes (Fig. 2). The characteristics bands of pristine PES
bar to reach a steady flow rate and measured at 3 bars. The feed and porous support were centered at 1485 and 1577 cm
1 (benzene rings),
permeate salt concentrations were determined by measuring water 1320 cm
1 (C–SO2–C), 1148 cm
1 (SO2) and 1104 cm
1 (C–O–C)
conductivities with a Thermo Scientific Orion Star A212 benchtop Con- [47–49]. After the first polyamide deposition cycle, we observed the
ductivity Meter. Rejection rates of the TFC membranes were calculated presence of new peaks centered at 1656, 1609 and 1538 cm
1. These
using the following equation (5): peaks corresponded to amide II, aromatic amide and amide I structures,
respectively [50]; indicating the formation of polyamide after one
 
Cp deposition cycle. The intensities of these amide-related peaks were
Rejection rate ¼ 1
*100 (5)
Cf relatively low when compared to the intensity of bands of characteristic
to PES porous support. As the number of deposition cycles increased from
where Cp and Cf are the solute concentrations in the permeate and feed one to five, we observed that the amide-related peaks overlapped with
solution, respectively. the benzene peak of PES at 1577 cm
1 and the relative intensities of both
C–SO2–C and SO2 peaks centered at 1320 cm
1 and 1148 cm
1 were
3. Results and discussions lower than those of amide-related peaks. This indicated that the PES
porous support layer was fully covered by polyamide after five deposition
3.1. PES support layers from spray-assisted NIPS

PES support layers are usually fabricated over 3 days. A dope solution
is formulated by stirring/mixing for 24 h to ensure full dissolution of the
PES [33,34], followed by a degas step that could take up to 24 h for
releasing air bubbles trapped inside the viscous dope solution [34–37].
Upon degassing, the well-rested dope solution is then cast into a wet PES
film. This wet film is then immersed in a water bath for 24 h to enable
polymer coagulation whilst ensuring complete solvent exchange [34,37,
43,44].
Here we halved this time-consuming fabrication protocol using our
spray-assist technique. In our approach, we used the same time as per the
traditional method (24 h) to formulate the dope solution. However, we
obviated the degas step in our protocol as air bubbles could still be
encapsulated in the dope solution droplets during spray coating, this has
been shown in our previous work [31]. We loaded this dope solution into a
spray gun and used 4 bar of nitrogen to break up this viscous solution into
droplets that were deposited on top of a glass plate, yielding a PES-Cyr-
ene™ wet film in 10 min. Once this wet film was formed, we deployed Fig. 1. Surface morphologies of PES structures fabricated by NIPS triggered by
spray-assisted NIPS over 5 cycles of water deposition to enable polymer (a) spray-assist technique and (c) water bath immersion. Cross section of PES
coagulation within 10 min (Scheme 1). Our approach to fabricate PES structures fabricated by NIPS triggered by (b) spray-assist technique and (d)
support layers in this work is different from our previous protocol [31]. water bath immersion.

4
S. Lin et al. Advanced Membranes 4 (2024) 100080

coating and our spray-assist techniques. After deconvolution of the C 1s

high-resolution scans of polyamides studied here, we observed four peaks
(Fig. S3) centered at 288.5 eV, 287.9 eV, 285.6 eV and 284.6 eV. These
peaks could be ascribed to O– – C–O, O– – C–N, C–N and C–C/C–H,
respectively [54,55]. The positions of these peaks were not affected by
solvent choice and fabrication technique. However, the content of each
species varied as a function of crosslinking degree i.e., fabrication tech-
nique across all polyamide samples studied here. According to Scheme 1,
O–– C–N group was introduced by the amide forming reaction between
acyl chloride in TMC and amine groups in MPD, O– – C–O group was
formed by hydrolysis of unreacted acyl chlorides in TMC monomers.
With a crosslinking degree of 55.5 %, polyamides fabricated by
dip-coating using n-hexane contained 5.7 % C– – O–O and 8.9 % O– – C–N.
As crosslinking degree increased to 82.0 % in polyamide fabricated from
five cycles of spray-assisted deposition using CPME, this polyamide only
contained 1.5 % of C– – O–O and 10.7 % of C– – O–N. This indicated that
spray-coated polyamide was more crosslinked than dip-coated poly-
Fig. 2. FTIR spectra of pristine PES porous support (black), polyamide TFC
membranes fabricated with one (red), two (blue), three (green), four (purple)
amide. The higher crosslinking degree in spray-coated polyamide could
and five (yellow) spray cycles of polyamide deposition, and by dip coating be attributed to the use of CPME as organic solvent [32], as CPME is more
(dark purple). soluble in water when compared to n-hexane and the required use of
more TMC in CPME to yield dense, selective polyamide films [40,54,56].
cycles. This was similar to changes in FTIR spectra as a function of
deposition repetition reported previously [22]. 3.3. Surface morphology of TFC membranes fabricated by spray coating
We also determined the elemental composition and chemical binding
information in polyamide TFC membranes studied here from XPS survey We observed that the polyamide layer fabricated via dip-coating using
and high-resolution scans, respectively. The atomic percentages of oxy- n-hexane comprised of crumpled ridges and valleys (Fig. S4), the thick-
gen, carbon and nitrogen in these membranes were determined using ness of this polyamide layer was around 250 nm. This ridge-valley
survey scans (Table 1). Theoretically, the O/N ratio of a fully crosslinked structure could be attributed to the uneven distribution of interfacial
polyamide with 100 % crosslinking degree is 1, while a fully linear polymerization reaction heat [17,57]. Switching to our spray-assisted
polyamide chain with 0 % crosslinking degree is 2 [51]. The O/N ratio of technique, when water-MPD droplets and CPME-TMC droplets encoun-
the polyamide selective layer fabricated using n-hexane as the organic tered each other on the PES porous support layer, a thin polyamide film
solvent via the conventional approach of dip coating was 1.35, indicating was formed in a confined area between the bulk water droplet and bulk
a crosslinking degree of 55.5 %. As TMC concentration was increased to organic droplet. This narrow interface layer is favorable for suppressing
3 wt% for spray-assisted deposition of CPME-based solutions, with one the polyamide layer from growing thicker and the limited amount of
cycle of MPD and TMC deposition, the atomic composition of resultant reactants in each droplet provided precise control of the diffusion and
polyamide film was more similar to that of a pristine PES membrane reaction behaviors [58]. As CPME was used as organic phase here in this
[52]. The O content was highest amongst all samples here (18.1 %), study, its higher water solubility and lower interfacial tension (when
probably due to the O–– S–– O functional group in PES and C– – O group in compared to n-hexane) can promote MPD diffusion into the reaction
polyamide. This indicated that the first layer of polyamide did not fully zone, allowing faster thin film formation [59]. Similar results was re-
cover the PES porous support. This was validated with SEM in the next ported when using acetone-hexane co-solvent as organic phase [60]. The
section. Subsequent deposition of polyamide on to the initial polyamide resultant thinner and more lose polymer structure is favorable to higher
layer yielded an O/N ratio of 1.19 and crosslinking degree of 74.4 %. The permanence [61].
O/N ratio was reduced from 1.19 to 1.13 after the fifth deposition cycle We also attempted to reduce the amount of TMC required in inter-
and the crosslinking degree reached a value of 82.0 %. The reductions in facial polymerization. With only 1 wt% TMC in CPME, the surface pores
O/N ratio and increments in crosslinking degree could be ascribed to of PES support layers could not be fully covered even with 4 deposition
prolonged reaction time as spray deposition cycles increased from two to cycles and the surface of the resultant polyamide layer contained cracks
five. This was similar to trends reported elsewhere when prolonged re- (Fig. S5). With 5 deposition cycles, we could still observe surface cracks
action duration enhanced crosslinking degree that also led to an increase on the top of the selective polyamide layer. Although the 5–10 μm PES
in polyamide layer thickness [53]. surface pores were covered by the polyamide layer, the surface of this
The XPS survey scans and C 1s high-resolution scans (Figs. S2 and S3) polyamide layer was porous and contained <100 nm pores. These pores
further confirmed the formation of polyamide via conventional dip might lead to low rejection rates. The reason for such porous polyamide
is the insufficient TMC in CPME solution. We showed that 3 wt% of TMC
is required to yield dense selective polyamide films when CPME was used
Table 1 as the organic phase in our previous work [32].
Atomic percentages, O/N ratio and crosslinking degree of TFC membranes When TMC concentration in CPME was increased to 3 wt%, we
studied here in this work. observed that the surface pores of the porous PES support layer were not
Polyamide type Number of Atomic composition O/N Crosslinking
fully covered after one polyamide deposition cycle (Fig. 3a–b). Poly-
spray ratio degree amide accumulated around the edge of the surface pores and the thick-
C N O
cycles nesses of this polyamide structures were ~100 nm. With two deposition
Conventional 0 74.6 10.8 14.6 1.35 55.5 % cycles, we observed the formation of the ridges and valleys structure of
dip coating polyamide that fully covered the surface pores. The thickness of this
Spray coating 1 76.6 5.36 18.1 3.38 – polyamide layer was ~180 nm. The ridges and valleys structures were
2 76.6 10.7 12.7 1.19 74.4 % refined after three and four cycles of polyamide deposition, while poly-
3 76.9 10.7 12.4 1.16 77.7 % amide film thickness increased to ~250–380 nm (Fig. 3), similar to ob-
4 77.6 10.4 11.9 1.14 80.0 % servations elsewhere with both large ridges and valley structure and
5 77.0 10.8 12.2 1.13 82.0 %
globular projections [22]. Interestingly, here we also observed the

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S. Lin et al. Advanced Membranes 4 (2024) 100080

Fig. 4. AFM images of all TFC membranes fabricated via a) conventional

method and b-f) spray assist method, spray cycle increased from b) 1 spray to f)
5 sprays.

After one cycle of spray-assisted polyamide deposition, the surface

roughness was only reduced by 17.2 %, to 149.2 nm. As observed in SEM
micrographs, the large pores (<5 μm) of the PES porous support layer
were not fully covered by the polyamide layer. With two cycles of
polyamide deposition, the surface of the PES support layer was fully
covered by polyamide (Figs. 3c and 4c). This reduced the surface
roughness by 75.4 %, to 44.22 nm. The surface roughness of polyamide
TFC membranes increased by 13.5 %, to 50.21 nm, with five polyamide
deposition cycles. Chowdhury et al. reported similar thicken polyamide
layer formed by electrospraying technique, in their result, each layer of
polyamide film cannot attach to the previous layer perfectly and will
create hollow structures within different layers, which then increase the
Fig. 3. SEM images of TFC membranes fabricated via spray-assist method, surface roughness as the number of scans increased [21]. Similar in-
surface scan shown on the left-hand side and cross-sectional scan shown on the creases in surface roughness were also observed in polyamide selective
rigth-hand side. a, b) 1 Spray; c, d) 2 Sprays; e, f) 3 Sprays; g, h) 4 Sprays; i, j) layers fabricated by molecular layer-by-layer assembly [20]. Here it is
5 Sprays. important to highlight that although the surface roughness of spray
coated polyamide membranes increased from 44.22 nm to 50.21 nm after
formation of partially hollow polyamide layers after three to four cycles 2–5 cycles of deposition, the overall surface roughness of our
of polyamide deposition. Such polyamide structures are characteristic of spray-coated polyamide membranes was still 16–26 % lower than that of
enhanced water-organic phase dissolution rates that accelerate MPD dip-coated variants (59.99 nm). This reduction in surface roughness
diffusion [40,62], and similar to those formed by electrospraying tech- could potentially prolong the typical lifespan of such membranes (2–4
nique [21]. Similar layer thickness increment was also reported previ- years) [66]. This is because reducting membrane surface roughness can
ously using layer-by-layer interfacial polymerization method, and such mitigate fouling [67–71] and consequently enhance membrane lifespan
hollow and sack-like structure is favorable for permeance increment [22, [72,73].
63]. With five polyamide deposition cycles, the thickness of the resultant
polyamide layer reached 550 nm (Fig. 3j). This could attribute to longer 3.4. Desalination performance of all TFC membranes
reaction durations and more monomeric reactants deposition [53].
Apart from tailoring surface morphology of TFC membranes, here we TFC membranes comprising a fully aromatic polyamide selective
also observed that spray-assisted interfacial polymerization also layer fabricated using MPD and TMC are mostly deployed for desalina-
impacted on surface roughness of polyamide selective layers (Fig. 4 and tion [65]. The separation performances of such TFC membranes are
S6). The surface roughness (root mean square, RMS) of the pristine PES dependent on surface morphology, chemical composition and roughness
porous support layer was 180.1 nm (Fig. 4a). The sizes and structures of [17,21,65]. In this study, we tested polyamide TFC membranes that were
surface PES pores were similar to those observed in SEM (Fig. 2a). When fabricated by spray coating and dip coating against 2000 ppm NaCl water
a polyamide layer was deposited on top of the PES porous support layer solution at 4 bar pressure. The water permeance and NaCl rejection rate
using the conventional method of dip-coating and n-hexane as the of the polyamide TFC membrane fabricated via dip coating using
organic phase, the surface roughness of the resultant polyamide-TFC n-hexane reached 1.71 L m
2 h
1 bar
1 and 92.3 % (Fig. 5), similar to
membrane was reduced to 59.99 nm (Fig. S6), similar to reports else- membranes fabricated from this approach reported elsewhere [31].
where [64,65]. Meanwhile, the water permeance of polyamide membranes fabricated

6
S. Lin et al. Advanced Membranes 4 (2024) 100080

Table 2
TFC membrane RO performance comparison.
Monomer IP method Organic Rejection Permeance Ref
combination solvent (L m
2 h
1
bar
1)

MPD-TMC Conventional n-hexane 92.3 % 1.71 This

work
MPD-TMC Conventional n-hexane 90 % 1.75 [80]
MPD-TMC Conventional Isoparrafin 95 % 1.875 [79]
MPD-TMC Conventional Ionic 98.2 % 0.74 [78]
liquid
MPD-TMC Conventional Ionic 96.8 1.09 [59]
liquid
MPD-TMC Conventional Xylene 99.8 % 1.57 [40]
MPD-TMC Conventional Toluene 99.9 % 1.59 [40]

MPD-TMC Spray-assist CPME 94.4 % 2.32 This

work
MPD-TMC Electrospray n-hexane 94 % 14.7 [21]
MPD-TMC Electrospray n-hexane 84.7 % 1.70 [24]
MPD-TMC mLbL Toluene 95.7 % 1.39 [19]
MPD-TMC mLbL Toluene 98.2 % 1.48 [20]
Fig. 5. Pure water permeance and NaCl rejection of all membrane samples in MPD-TMC Free- n-hexane 93.3 % 4.06 [17]
this stuey against 2000 ppm NaCl-water solution. interfacial

with CPME and dip-coating reached 1.51 L m
2 h
1 bar
1 and the NaCl
polymerization typically reduced water permeance due to the increased
rejection rate was increased to 97.8 % [32]. The use of CPME as solvent
water-organic solubility of such solvents and this would thicken the
for IP via dip-coating reduced the permeance of resultant TFCs by 11.7 %
polyamide selective layer. This limitation was overcome here with the
whilst enhancing NaCl rejection by 5.5 % [32]. This reduction in per-
spray-assist deposition technique that alleviated the layer thickening
meance and increment in NaCl rejection was ascribed to higher cross-
effect associated with using solvents with improved water solubility [22,
linking degrees and thicker selective layer [74,75], in membranes
40]. Nonetheless TFC membranes comprising MPD-TMC polyamide se-
produced in CPME (79.9 % crosslinking degree and ~500 nm thickness).
lective layers with sub-10 nm thickness and sub-20 nm roughness
The crosslinking degree in dip-coated membranes fabricated with
fabricated from electrospraying [21] and free interfacial polymerization
n-hexane was only 52.4 %, with a thickness of ~250 nm. When switching
[17] presented higher water permeances at 14.7 and 4.06 L m
2 h
1
to spray-assist method, the water permeance and NaCl rejection rate of a
bar
1 and similar NaCl rejection rates.
TFC membrane fabricated with one polyamide deposition cycle using 1
wt% TMC in CPME reached 9.13 L m
2 h
1 bar
1 and 12.5 %. With five
4. Conclusion
polyamide deposition cycles, the water permeance and NaCl rejection
rate of such membranes reached 5.17 L m
2 h
1 bar
1 and 32.1 %
In summary, in this study, we have successfully exploited the spray-
(Table S1). This high permeance and low rejection were mainly due to
assisted deposition technique to fabricate both the selective and porous
the defective selective layer (Fig. S5).
support layers of a TFC membrane using an automated spraying system.
When using 3 wt% of TMC in CPME, the water permeance of a TFC
This reduced TFC membrane fabrication time from 4 days to 1 day and
membrane fabricated by one cycle of spray-assisted polyamide deposi-
40 min. We also showed that spray-coating can overcome the polymer
tion increased to 8.84 L m
2 h
1 bar
1, but its NaCl rejection rate only
thickening effect of organic solvents that are more water soluble than n-
reached 19. 3 %. This was most possibly due to a defective selective layer
hexane that typically reduces water permeances. These findings could
that did not cover the surface pores of the PES support as shown in Figs. 3
potentially benefit and improve the sustainability of large-scale produc-
and 4. As the polyamide deposition cycles increased from two to five, the
tion of polyamide TFC membranes for desalination.
permeances of resultant membranes reduced from 2.32 L m
2 h
1 bar
1
to 1.48 L m
2 h
1 bar
1, while the NaCl rejection rates increased from
CRediT authorship contribution statement
94.4 % to 98.3 %, respectively (Fig. 5). The increase in NaCl rejection
rates could be attributed to an increase in crosslinking degree, from 74.4
Shiliang Lin: Writing – review & editing, Writing – original draft,
% to 82.0 %, and the sealing of PES surface pores with more spray-
Visualization, Validation, Methodology, Investigation, Formal analysis,
assisted polyamide deposition cycles. Meanwhile the decrease in water
Data curation, Conceptualization. Yanqiu Zhang: Writing – review &
permeances could be ascribed to the formation of thicker selective layers
editing, Visualization, Validation, Methodology, Investigation, Formal
[17,76]. Similar trends were also reported for TFC membranes
analysis, Conceptualization. Lu Shao: Writing – review & editing,
comprising fully aromatic polyamide selective layers fabricated via the
Methodology, Investigation, Formal analysis. Cher Hon Lau: Writing –
molecular layer-by-layer [20] and electrospraying techniques [21,24].
review & editing, Writing – original draft, Visualization, Validation,
To evaluate the long-term performance of polyamide-PES TFC with 2
Resources, Project administration, Methodology, Investigation, Formal
cycles of deposition, we followed published protocols [77] to extend the
analysis, Data curation, Conceptualization.
desalination test to 8 h. The long-term permeances of such TFC mem-
brane averaged at 2.32 L m
2 h
1 bar
1 and a rejection above 94.39 %
Declaration of competing interest
(Fig. S7).
Compared to the TFC membrane fabricated using dip coating and n-
The authors declare that they have no known competing financial
hexane, here we also observed that the TFC membrane fabricated from
interests or personal relationships that could have appeared to influence
two cycles of spray-assisted polyamide deposition showed a better
the work reported in this paper.
rejection rate of 94.4 % and a 35.7 % higher water permeance, reaching
2.32 L m
2 h
1 bar
1 (Table 2). Here, it is important to highlight that in
Acknowledgement
current literature, the use of organic solvents other than n-hexane, for
e.g., ionic liquid [78,79], xylene or toluene [40] in interfacial
We acknowledge financial funding from the Royal Society

7
S. Lin et al. Advanced Membranes 4 (2024) 100080

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S. Lin et al. Advanced Membranes 4 (2024) 100080

Shiliang Lin received his Bachelor of Science degree in Chem- Lu Shao is currently a full professor in School of Chemistry and
ical Engineering at the Wuhan University of Technology in Chemical Engineering at Harbin Institute of Technology (HIT)
2018, and Master degree in Advanced Chemical Engineering at in China. He received his PhD (2005) from National University
the University of Edinburgh in 2019. He continued his aca- of Singapore. Before joining HIT in 2006, he had worked as the
demic career as a PhD candidate at the same institute under the assistant project manager in C-PAK Company in Singapore. His
guidance of Dr. Cher Hon Lau. His research interests are mainly research interests are advanced separation membranes and
focused in fabrication of green thin-film composite membrane membrane processes, with a particular focus on energy and
its application in desalination. environmental applications. Prof. SHAO is the author of more
than 130 publications in Journal of Membrane Science, Energy
Environmental Science, Materials Today, Nature Communica-
tions, MATTER, Advanced Energy Materials, Advanced Func-
tional Materials, Materials Horizons, Journal of Materials
Chemistry A … with the SCI citations more than 5000 times and
H-index of 42. He was awarded New Century Excellent Talents
in University (China) in 2011 and elected as Fellow of the Royal
Society of Chemistry (FRSC, UK) in 2020.
Yanqiu Zhang is currently an associate professor at Harbin
Institute of Technology and obtained her Ph.D. degree (2020)
from the School of Chemistry and Chemical Engineering, Har-
Cher Hon Lau is currently a Senior Lecturer at The University of
bin Institute of Technology, China. She received her Master's
Edinburgh, School of Engineering. His research background is
degree (2015) from the School of chemistry, Northeast Normal
in materials science, with particular focus on separation appli-
University, P. R. China. Her current research interests are
cations. He has been active in research on separation science
focused on membrane separation and advanced two-
since 2008. He is a graduate of Ngee Ann Polytechnic, Flinders
dimensional materials towards environmental remediation.
University and The National University of Singapore in various
courses ranging from Electronics and Computer Engineering to
Nanotechnology to Chemical and Biomolecular Engineering.
His research has been commercialized in China and Australia.
He has published more than 60 scientific research papers in
journals such as Science, Nature Communications, Science
Advances, Angewandte Chemie International Edition, PNAS
etc. His research has been cited more than 5000 times, resulting
in a h-index of 37.

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