Advances in Colloid and Interface Science 276 (2020) 102100

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Advances in Colloid and Interface Science

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

Historical Perspective

Reverse osmosis membrane fabrication and modification technologies

and future trends: A review
Ruth Habte Hailemariam a, Yun Chul Woo b,⁎, Mekdimu Mezemir Damtie a, Bong Chul Kim c,
Kwang-Duck Park b, June-Seok Choi a,b,⁎
a
Department of Civil and Environment Engineering, University of Science and Technology, (UST), 217, Gajeong-Ro, Yuseong-Gu, Daejeon 34113, Republic of Korea
b
Department of Land, Water and Environment Research, Korea Institute of Civil Engineering and Building Technology, 283 Goyang-Daero, Ilsanseo-Gu, Goyang-Si, Gyeonggi-Do, 10223,
Republic of Korea
c
Water Environment Center, Environmental Technology Division, Korea Testing Laboratory (KTL), 87, Digital-Ro 26-Gil, Guro-Gu, Seoul 08389, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: Reverse osmosis (RO) is the most widely used technology in water treatment and desalination technologies for
27 December 2019 potable water production. Since its invention, RO has undergone significant developments in terms of material
Available online 27 December 2019 science, process, system optimization, methods of membrane synthesis, and modifications. Among various ma-
terials used for the synthesis of an RO membrane, the polyamide thin-film composite (PA-TFC) is by far the
Keywords:
most common, owing to its excellent water permeability high salt rejection, and stability. However, a tradeoff
RO membrane fabrication
Surface modification
between membrane permeability and salt rejection and membrane fouling has been a major hindrance for the
PA-TFC effective application of this membrane. Thus, a broad investigation has been carried out to address these prob-
Co-solvent-assisted interfacial polymerization lems, and among which co-solvent interfacial polymerization (CAIP) and the surface modification of substrates
and active layers of RO membrane have been the most effective approaches for controlling and improving the
surface properties of the PA-TFC membrane. In this review paper, the problems associated with the RO mem-
brane processes and strategies has been discussed and addressed in detail. Furthermore, as the focus of this re-
view, the major advancements in the strategies used for enhancement of RO membrane performance through
CAIP, and surface modifications were scrutinized and summarized.
© 2019 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. Reverse osmosis membrane process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2. Major process in reverse osmosis plant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.3. Challenges associated with RO process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.3.1. Fouling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.3.2. Chlorination. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.3.3. Brine disposal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3.4. Boron removal. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3.5. Tradeoff between salt rejection and permeability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3. Reverse osmosis membrane material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4. Strategies to improve PA-TFC RO membrane performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4.1. Addition of co-solvent organic phase during interfacial polymerization (CAIP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4.2. RO membrane surface modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4.2.1. Modification of support layer of PA membrane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4.2.2. Modification of active layer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

⁎ Corresponding authors at: Department of Land, Water and Environment Research, Korea Institute of Civil Engineering and Building Technology, 283 Goyang-Daero, Ilsanseo-Gu,
Goyang-Si, Gyeonggi-Do 10223, Republic of Korea.
E-mail addresses: yunchul84@gmail.com (Y.C. Woo), jschoi@kict.re.kr (J.-S. Choi).

https://doi.org/10.1016/j.cis.2019.102100
0001-8686/© 2019 Elsevier B.V. All rights reserved.
2 R.H. Hailemariam et al. / Advances in Colloid and Interface Science 276 (2020) 102100

5. Conclusion and prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

1. Introduction
Nomenclature
Scarcity of drinking water is one of the biggest problems in the world
Δp Transmembrane pressure difference that must be solved urgently. Population growth, industrialization, ur-
Δπ Osmotic pressure difference banization, and climate change have been aggravating freshwater crisis
A Intrinsic water permeability coefficient all over the world. Over the last few decades, it has become evident that
ACA 6-Aminocaproic acid because of a steadily increasing demand, scarcity of fresh water is be-
BSA Bovine serum albumin coming a threat to the sustainable development of human society [1].
BSR Boron-selective ion exchange resin Moreover, the discharges from industrial processes are contaminating
BWRO Brackish water reverse osmosis the natural water resources, posing serious environmental problems.
CA Cellulose acetate Therefore, the provision of clean water is critical and should be attained
CAIP Co-solvent interfacial polymerization to meet the increasing water demand. As water resources become
CaSO4 Calcium sulfate scarce, the demand for water purification technologies is gradually in-
Cl2 Chlorine gas creasing. Seawater desalination and wastewater reuse are widely con-
ClO Hypochlorite ion sidered as promising solutions to augment water supply and alleviate
DMF N,N-dimethylformamide water scarcity. Given the fact that N97% of global water resources are
DMSO Dimethyl sulfoxide seawater, seawater desalination has become an important and a prom-
ED Electrodialysis ising water purification methodology [2].
ERD Energy recovery devices Desalination is the process of removing salt, and other minerals and
GA Glutaraldehyde contaminants from seawater, brackish water, and wastewater effluent,
GO Graphene oxide to obtain clean water for domestic consumption, agriculture, and indus-
HCIO Hypochlorous acid trial application. Desalination has been used for the production of pure
HMPA Hexamethyle phosphoramide water from the feed of 67% for seawater, 19% for brackish water, 8%
IP Interfacial polymerization for river water, and 6% for other wastewater, as shown in Fig. 1(a) [3].
J Water flux Based on the separation mechanism, desalination technologies can be
LMH L/m2/h categorized into phase-change (thermal) and membrane-based separa-
MD Membrane distillation tion processes. The phase-change separation process removes salts from
MED Multi-effect distillation water by a continuous process of evaporation and condensation. This
MF Microfiltration process includes multi-effect distillation (MED), multi-stage flash
MOF Metal–organic framework (MSF), and vapor compression distillation (MVC). The membrane-
MPD M-phenylenediamine based desalination uses a membrane—reverse osmosis (RO), nanofilt-
MVC Vapor compression distillation ration (NF), and electrodialysis (ED)—that acts as a filter to the water
NaOCl Sodium hypochlorite and allows it to pass through, while retaining salt and other minerals.
NF Nanofiltration As shown in Fig. 1(b), N50% of desalination plants in the world use RO
NMP Methylpyrrolidone technology because of its simplicity, energy efficiency, and relatively
PA Polyamide low operational cost [4].
PAN Polyacrylonitrile Membrane separation technology is the most popular technology for
PA-TFC Polyamide thin-film composite separating a wide range of fluids, including gas, oil, and water. Some of
PEG Poly(ethylene glycol) the advantages of using membrane over other technologies include rel-
PEGA Poly(ethylene glycol) acrylate atively low operational energy requirement, easy upscaling, simple op-
PES Polyethersulfone erational process, and no requirement of additional chemicals. Based on
PP Polypropylene the driving force, membranes can be categorized into pressure driven or
PPO Polyphenylene oxides non-pressure driven process. Non-pressure driven process the driven
PSU Polysulfone force can be temperature (membrane distillation (MD) [5] or electrical
RO Reverse osmosis potential (ED). Under a pressure-driven process based on the retention
SDS Sodium dodecyl sulfate size and pore size, membranes are divided into four groups, microfilt-
SEC Specific energy consumption ration (MF, 0.1–2.0 μm), ultrafiltration (UF, 2–100 nm), nanofiltration
SFIP Support-free IP (NF, 1–10 nm), and RO (b1 nm) [4].
SPGE Sorbitol polyglycidyl ether From a pressure-driven process, the widely used membranes in
SR Salt Rejection water and wastewater treatment plants are the RO and NF membranes.
SWRO Seawater reverse osmosis Numerous research works have been conducted for the development of
TFC Thin-film composite RO membrane. Among other materials, polyamide (PA) is commonly
TFN Thin-film nanocomposite used in RO membrane fabrication. PA thin-film composite (PA-TFC)
TMC Trimesoyl chloride membranes have undergone remarkable development after the concept
TMP Transmembrane pressure of interfacial polymerization (IP) was introduced. It is dominating the
UF Ultrafiltration world's membrane market owing to its excellent salt rejection (SR) ca-
WHO World Health Organization pability and high water flux [6], and due to the fact that the layer of PA-
ZLD Zero liquid discharge TFC membrane can be controlled independently to attain the desired
 R.H. Hailemariam et al. / Advances in Colloid and Interface Science 276 (2020) 102100 3

Fig. 1. (a) Feed-water used in the desalination industry around the world in percentage [3], and (b) global desalination plants capacity for different technology [3].

permeability and rejection. In addition, they can withstand high tem- pressure becomes greater than the osmotic pressure (Δp N Δπ), the
perature, are operable over vast pH differences (1−11), offer excellent feed water passes through the membrane, leaving salt and other
mechanical strength, are stable under high pressure compaction and bi- minerals behind, and comes out as purified water (Fig. 2). The two
ological attacks, and incur relatively low overall cost [7]. parameters governing the performance of the RO membrane are
However, RO membrane suffers from a tradeoff between mem- water flux and salt rejection [9].
brane permeability, and salt rejection/selectivity, fouling, and
chlorination problems. High permeability is always associated
with low salt rejection, which is a major hindrance in the investi- J ¼ AðΔp−ΔπÞ ð1Þ
gation of PA-TFC membrane with high permeability and high con-
stant salt rejection. Likewise, fouling and chlorination have an
where J is the water flux, Δp is the transmembrane pressure (TMP)
adverse effect on the membrane performance. When accumulated
difference, Δπ is the osmotic pressure difference between the feed
on the membrane surface, foulants lead to a significant reduction
water and the permeate water, and A is an intrinsic water permeabil-
in permeability and selectivity, and addition of chlorine is the
ity coefficient that describes the membrane [4].
most convenient approach to remove these foulants from the
Over the last few decades, several improvements have been made
membrane surface and restore membrane performance. However,
in the preparation of RO membranes from different materials. Be-
chlorine can react with PA, which lead to a significant reduction
cause of these improvements, the market for RO-based desalination
in membrane performance [8].
is steadily increasing. These advances also enabled the reduction of
To address such bottlenecks, researchers have attempted in various
energy consumption and cost for pure water production [10]. Spe-
ways to tackle the challenge. So far, several review articles addressing
cific energy consumption (SEC), which is expressed in kWh/m 3 of
the issue of RO membrane fabrication and performance-enhancement
the product water, is the most substantial parameter used to charac-
strategies have been contributed. However, the articles have paid lim-
terize the performance of the RO membrane process. SEC for the RO
ited attention to the significant contribution already made via co-
process mainly depends on operating conditions such as feedwater
solvent IP (CAIP). In lieu of the limited contribution, this review ad-
salinity, recovery rate, efficiency of intake and product water
dresses and delivers special emphasis on membrane synthesis by CAIP
pumps, and energy recovery systems. There are different approaches
approach. This review also provides a brief insight into the RO process,
aimed at reducing the total energy consumption; for instance, devel-
the type of material used for membrane fabrication, and the surface
oping highly permeable membranes, and using highly efficient pres-
properties of each membrane type. In addition, the IP of PA-TFC RO
sure pumps and energy recovery devices (ERD). ERD has become an
membrane, and its advantage and drawbacks are discussed in detail.
indispensable part of the seawater reverse osmosis (SWRO) desali-
Moreover, as the focus of this article, the strategies used for surface
nation system, as it recovers the hydraulic energy from the highly
modification of PA-TFC membrane for the improvement of membrane
pressurized reject brine, thereby reducing energy consumption sig-
performance are reviewed.
nificantly [11].
2. Background

2.1. Reverse osmosis membrane process

Recently, RO has been the most widely used technology for both
water treatment and desalination technologies in the world. RO is
used in desalination industries to produce clean water suitable for
drinking, agriculture, and industries, by removing salts, minerals, and
ions from the feed water. The efficiency of RO process depends on the
operational parameters and the feed water characteristics. In RO desali-
nation technology, external pressure is applied to a stream of water to
overcome the natural osmotic pressure.
In naturally occurring osmosis process, the solvent moves from
the area of low to high solute concentration to equalize the solute
concentration on both sides of the membrane, which produces the
osmotic pressure. The applied pressure on the RO membrane is
used to reverse the flow direction of solvents. When the applied Fig. 2. Schematic illustration of reverse osmosis.
4 R.H. Hailemariam et al. / Advances in Colloid and Interface Science 276 (2020) 102100
2.2. Major process in reverse osmosis plant
An RO desalination plant consists of four major processes feed water
pre-treatment, pressurization/high-pressure pumps, membrane sepa-
ration, and permeate post-treatment [10].
Pre-treatment plays a critical role by making the feed water compat-
ible with the RO membrane. Untreated seawater contains various con-
taminants, such as suspended solids, colloidal maters, microorganisms,
and other impurities, which can cause scaling, fouling, and premature
degradation of the membrane upon coming in contact with the mem-
brane surface. During the pretreatment, the feed water is treated by
screening, filtration, chlorination, pH adjustment, microfiltration, and
ultrafiltration, and by adding chemicals to control fouling and scaling.
The choice of pretreatment process depends on factors such as feed
water, space availability, and RO membrane requirements. Pretreat-
ment is used to maximize the efficiency and operating life of an RO sys-
tem by optimizing product flow, salt rejection, recovery, and overall
operating cost [12].
High-pressure pumps provide the pressure needed to pump
the pretreated water and overcome the osmotic pressure, so that the
water can pass through the membrane. The required pressure for
the RO process depends on the type of feed water that is to be treated,
for instance, the pressure needed for brackish water ranges from 15 to
25 bar and for seawater it ranges from 50 to 80 bar. The semi-
permeable membrane should withstand the pressure drop that occurs
during the process [13].
Membrane separation is the filtration process performed by a semi-
permeable membrane that allows pure water to pass through while
rejecting salts, ions, and organic molecules in the feed water. This
semi-permeable membrane is the fundamental part of RO-based sepa-
ration. RO membrane modules used for large-scale plant application
and the most commonly used membrane module configurations are
the spiral wound module and the hollow fiber module.
At the post-treatment stage, the permeate water from the RO unit is
stabilized and prepared for distribution, and the treatment depends on
the product water application. The membrane removes most of the dis-
solved solids from the feed water; however, a small percentage of salt
may pass through the membrane and remain in the permeate water. Be-
cause of this, post-treatment is needed to treat the remaining impurities
before the product water is delivered to the distribution system. The
post-treatment process includes pH adjustment, degasification of car-
bon dioxide, addition of lime, and disinfection using sodium hypochlo-
rite and remineralization.
2.3. Challenges associated with RO process
The major challenges in the application of RO membrane to be ad-
dressed through different membrane fabrication techniques, modifica-
tions, and system efficiency enchantment systems include scaling,
membrane fouling, chlorination, a tradeoff between permeability and
salt rejection, boron removal, and brine disposal.
2.3.1. Fouling
Membrane fouling is the deposition of unwanted material on the
surface or within the pore of the membrane. It must be pointed out
that membrane fouling restricted the desalination process. Fouling sig-
nificantly affects water flux, permeate quality, salt rejection, and mem-
brane performance. Moreover, it increases the operational cost and
shortens membrane lifespan. Thus, taking preventive methods to con-
trol membrane fouling is highly recommended as a critical way to
control the economics of the seawater RO desalination process. Fouling
can be reversible and irreversible, and the latter causes long-term
reduction of flux, which cannot be fully recovered by cleaning the mem-
brane. Membrane fouling is generally categorized into organic
fouling, inorganic fouling, colloidal/particulate fouling, and biofouling/
microbiological fouling [14]. Organic, inorganic, and colloidal fouling
Fig. 3. The sequence of events leading to the formation of biofilm [17].
can be reduced to a great extent using pretreatment process; however,
pretreatment alone is not enough to reduce biofouling [15] because the
accumulated microbial cells on the membrane surface can grow, in-
crease in number, and relocate (Fig. 3). Hydrophilicity, surface charge,
and surface roughness have a great impact on membrane fouling. Sur-
face roughness directly related to a membrane fouling as the mem-
branes with rougher surfaces are highly susceptible to fouling because
the smooth surface not allow the growth of foulant to adhere as easily
as does a textured surface. Overall, membranes with high hydrophilic-
ity, smoother surface, and low negative charge demonstrated better
fouling resistance [16].
Inorganic fouling or scaling in RO membrane is formed as the
purified water permeate passes through the membrane module, con-
centration of different soluble salts in the feed water increases, and con-
centrated four to ten times depending on the rejection efficiency and
operating recovery. When the dissolved salts exceed their solubility
limit, they start to precipitate and form a scale on the surface of the
membrane. Some of the compounds that can cause scaling deposition
on the membrane surface include calcium sulphate, calcium phosphate,
calcium carbonate, barium sulphate, and silica. Scaling leads to loss of
production, flux reduction, elevated energy consumption, increasing
total operating costs, and shortening of membrane life, which in return
affects the productivity of the RO process [18]. Pretreating feed water by
pH adjustment, cation–ion exchange, NF, or ultrafiltration (UF) process
helps to reduce scaling. Addition of antiscalants on the pretreatment
process helps prevent scaling by extending the solubility limits of the
scaling salts [19]. Modification of thin-layer polyamide by incorporating
graphene oxide (GO) helps prevent gypsum-induced scaling [20].
2.3.2. Chlorination
Among the techniques used to control membrane fouling of an RO
membrane, addition of chlorine is one of the most effective methods
for deactivating microbial growth in the feed water, which helps
lower chances of occurrence of membrane biofouling [21]. However,
using chlorine as a disinfectant are threatening for most of the PA-
based membranes eventually, it leads to impaired performance and
membrane degradation. Cl2 gas or NaOCl in the feed water form
hypochlorous acid or HCIO by hydrolyzing, and can be further
deprotonated and form a hypochlorite ion or ClO− [22]. From the PA
RO membrane sites, aromatic rings and amide nitrogen are highly sus-
ceptible to attacks by free chlorine (Fig. 4) [23]. After chlorination the
amide bond cleavage and N-chlorination lead to the structural changes
on the active polyamide layer, which causes loss of cross-linking density
of polyamide layer, reducing strength, and results in an irreversible deg-
radation on the membrane performance.
Several studies have been conducted to investigate the causes of im-
paired performance and membrane degradation changes in the poly-
amide membrane upon chlorination. Some of the strategies initiated
to develop chlorine-resistant polyamide membrane include an elimina-
tion of sites that are likely to be attacked by chlorine, protection
of chlorine-sensitive sites, and surface modification of the polymer
structure [24].
 R.H. Hailemariam et al. / Advances in Colloid and Interface Science 276 (2020) 102100
Fig. 4. Four approaches of active chlorine species for the attack the polyamide layer [4].
2.3.3. Brine disposal
Brine or brine-blowdown is the highly concentrated effluent
rejected from the desalination process. The effluent has higher salinity
than the feed seawater and contains high levels of total dissolved solids,
acids, organic compounds, anti-foulant, anti-scalants, and other chemi-
cals added during the pretreatment process [25]. The amount of concen-
trates from the desalination plant depends on the type of desalination
technology used, the feed-water salt concentration, and percentage re-
covery. These factors determine the choice of disposal method. Despite
the fact that membrane desalination can provide clean water, rejected
brine from desalination plants is a critical environmental issue. Conse-
quently, various environmental regulations related to brine disposal
have emerged in different parts of the world. Selection of a proper dis-
posal method is essential for the feasibility of the desalination industry.
Brine disposal methods include direct discharge into surface water,
evaporation ponds, land application, and deep well injection. Disposal
of brine into the sea is a preferable method when the desalination
plant is near to the shore. However, this type of disposal method
could degrade the physical and chemical characteristics of the water
body and its ecology [26]. The disposal of brine via evaporation pond
is used where oceanic discharge is not possible, and it is much more
suitable, especially for countries with a dry and warm climate. This dis-
posal method is recommended in places where the evaporation rate is
higher and a wider land area is available. In areas with higher disposal
rates or low rates of evaporation, this disposal method requires a large
area of land for operation. It is also necessary to seal the pond with im-
pervious liners (clay, PVC, Hypalon) to avoid risk of groundwater con-
tamination due to seepage [27].
After saturating the brine water with CaSO4 or silica, the electrodial-
ysis (ED) experiment is conducted to increase the concentration from
1.5–10% so that it significantly reduces the brine volume and cost of dis-
posal. However, the disadvantage of this approach is the precipitation of
CaSO4 on the membrane surface during the process. In another research
work, a pilot-scale ED plant was built to treat brine by circulating it
throughout the ED cell after passing it through a separate CaSO4 precip-
itator containing gypsum seeds, which in turn are used to precipitate
the excess CaSO4 from the solution [28]. Another case study used the
SAL-PROC technology as a means to minimize the waste discharge
from desalination plants, while extracting valuable chemicals from the
brine stream. In this process, multiple evaporations and cooling cycles
are added by chemical and mineral processing. The extracted valuable
chemical products can be found in the form of liquid, slurry, or crystal.
The high quality components recovered by this process include NaCl,
NaSO4, NaSO4, CaCO3, CaCl, Mg(OH)2, and gypsum [29]. The integrated
process of solar and evaporation ponds can significantly decrease the
desalination cost, while producing valuable minerals from concentrated
5
brine. The zero liquid discharge (ZLD) approach is used to recover water
and salt by ejecting liquid waste from brine. For a feasible application of
ZLD, a brine pretreatment process essential to increasing membrane
water recovery and reduce the operational cost of the ZLD process is
used [30].
2.3.4. Boron removal
With the recent rapid growth of RO membrane applications in sea-
water desalination, the issue of boron removal has come under the sci-
entific spotlight. Even though boron is crucial for the development of
humans, plants, and animals, an excess amount of boron can be toxic
and lead to serious health problems and environmental damage. As
per the World Health Organization (WHO) guidelines, the concentra-
tion of boron in drinking water should be below 0.5 mg/L [31]. For this
reason, adequate boron removal in water treatment technologies is cru-
cial for drinking water application. The percentage removal of boron
from seawater is not enough as boron exists in the form of uncharged
boric acid, which, like water, can easily pass through an RO membrane
[32]. Hence, the single-pass RO process is insufficient for boron removal.
Therefore, to remove boron to a desirable level, most of the seawater de-
salination plants are designed with the multipass reverse osmosis mem-
brane. However, the multipass RO process consumes additional energy
and results in over demineralization of the product water, and boron re-
moval optimization by RO membranes is important for better quality of
water production and reduction of energy consumption. Over the last
few years, several scientific studies have investigated the removal of
boron via the RO membrane. The pH and ionic strength of feed water
govern the removal of boron by RO. At neutral pH, boron exists in the
form of boric acid B(OH)3 and removal is achieved between only
40–80%. At high pH, however, boron is dissociated into negatively
charged borate (B(OH)− 4 ), and N99% of boron can be removed by RO
membranes [33]. Generally, boron can be more effectively removed at
pH 11 than at lower pH values [32].
Boron-selective ion exchange resin (BSR) is one of the most efficient
techniques for potable / drinking water, wherein the feed water passes
through high-pressure RO membrane followed by BSR. However, the
high cost, storage of chemicals for regeneration, and disposal of BSR
are the challenges that need to be resolved. The efficiency of boron re-
moval using commercial RO PA-TFC membranes is relatively lower
than other dissolved ions under similar operating conditions. For effec-
tive boron removal, multiple RO passes after certain pH adjustment of
the feed water is highly recommended.
2.3.5. Tradeoff between salt rejection and permeability
A tradeoff between salt rejection and permeability is another draw-
back of the currently available polymeric membranes. For instance,
higher salt rejection always comes with a lower permeate flux/perme-
ability, and vice versa. Therefore, it is a major obstacle to investigate
the PA-TFC membranes with high permeation property and high con-
stant salt rejection.
In the last few years, studies have been conducted by incorporating
nanoscale materials during the interfacial polymerization process to
overcome this tradeoff. A multiwall carbon nanotube–polyamide
(MWNT-PA) nanocomposite membrane was developed to enhance
the membrane performance by modifying the surface and eliminating
the tradeoff between water permeability and selectivity [34]. In another
work, inorganic polyamide nanocomposite membrane was prepared
using phenyltriethoxysilane on a UF PSU support with a promising
metal-alkoxide-assisted interfacial polymerization method. The pre-
pared membrane showed a two-fold increase in water flux compared
with the PA membrane with insignificant salt rejection loss [35]. The in-
corporated nanoparticles are a promising means to improve the proper-
ties of PA by modifying the membrane network structure due to its
tunable characteristics of size, shape, solubility, and hydrophilicity,
thus, increasing water permeability.
6 R.H. Hailemariam et al. / Advances in Colloid and Interface Science 276 (2020) 102100
As mentioned in the above section chlorination is the most com-
monly used disinfection process to control membrane biofouling. How-
ever, the chlorination has an effect on the water flux and salt rejection
performance of the membrane. During chlorination, the structural
changes on the active layer of the membrane cause the water flux to in-
creases due to the lower cross-linking density that facilitates the diffu-
sion of water through the membrane while reducing the salt rejection
performance [36].
3. Reverse osmosis membrane material
Polymeric RO membranes have controlled commercial applications
since the very beginning of RO desalination plant. Because of their tech-
nological maturity, polymeric membranes are easy to handle, inexpen-
sive to fabricate, and offer improved permeability and salt rejection
performance.
In 1959, Reid and Breton reported a hand-cast thin symmetrical cel-
lulose acetate (CA) film capable of separating salt from water. However,
the water flux was too small and not suitable for practical applications
[37]. Next, Loeb and Sourirajan developed the first reverse-osmosis
membrane from CA polymer, which made RO practical, and the mem-
brane was capable of rejecting salts and have a higher water flux [38].
CA polymer was the best material for RO membrane until 1969. Despite
that, CA membranes are limited to a relatively narrow pH range as the
acetate group in CA is susceptible to hydrolysis in both alkaline and
acidic conditions, susceptible to microbial attack / biofouling, and easily
compacted at high pressures [39].
It is noteworthy to mention that the first non-cellulosic asymmetric
membrane consisted of an aromatic hollow fiber polyamide (PA) mem-
brane developed by Richter and Hoehn [40]. This membrane was com-
mercialized by DuPont under the trade name, B-9 Permasep, for
application in brackish water desalination. Although it performed better
than the CA membrane, the PA membrane was highly susceptible to be
attacked by the presence of oxidizing disinfectants such as ozone and
chlorine after prolonged use. The invention of CA asymmetric mem-
branes played a significant role in water desalination, and significant
improvement has been accomplished over the years. Cellulosic poly-
mers (cellulose acetate, cellulose diacetate, etc.) and the most widely
used example of asymmetric membranes are linear aromatic PA mem-
branes [41].
Later on, Cadotte and Petersen prepared the first efficient thin-film
composite (TFC) membrane, which was one of the biggest technological
advancements in the history of RO processes. TFC membranes make RO
membranes economically feasible and applicable in large-scale desali-
nation plants. A typical TFC membrane is composed of an outer active
ultra-thin polyamide layer (0.1–1 μm), a porous middle-support
polysulfone (PSU), and a non-woven polyester fabric base. TFC is the
membrane most commonly fabricated via interfacial polymerization
(IP) [35,42].
IP is important for the development of membrane science and tech-
nology. The introduction of interfacial polymerization process is a key
technological breakthrough for the production of low-pressure mem-
branes with high water flux and salt rejection [6]. The IP process starts
by saturating the porous polymeric support layer in an aqueous solution
of m-phenylenediamine (MPD) followed by an organic trimesoyl chlo-
ride (TMC) solution [43]. Compared to cellulose acetate, polyamide
membrane is widely applied in the membrane industry as it performs
well under low pressure over a wide range of temperature and pH,
and has good stability under high-pressure compaction and biological
attacks. Furthermore, PA-TFC membranes are characterized by excellent
water permeability and high salt rejection due to their highly cross-
linked and ultra-thin polyamide skin layer. Thus, polyamide and related
membranes dominate membrane desalination technology [7,42,44].
However, use of polymeric membrane for wastewater and desalination
technology have faced some critical issues such as the tradeoff between
water permeability and salt rejection, and membrane scaling and
fouling in order to achieve a sustainable application of polymeric mem-
brane in desalination technologies. This has drawn the attention of re-
searchers toward improving membrane performance via various
strategies of membrane modification, to achieve simultaneous enhance-
ment of permeability and selectivity, as well as to synthesize PA-TFC
membrane with antifouling and chlorine-resistance properties. Thus,
synthesis of high-performance polymeric RO membrane has become
one of the focus research topics in the study of desalination.
Inorganic membrane in the membrane fabrication process has
drawn much attention because of its exceptional physical and chemical
properties, and high tunability and reusability. Its high stability has
made it an attractive alternative for challenging water treatment pro-
cesses such as for the feed water containing highly concentrated or-
ganics, radioactive substances, grease, and oil [45]. Moreover, they are
less susceptible to deterioration by microorganisms or bacteria, which
is the main reason for biofouling degradation, which makes it suitable
in applications where polymeric membranes are either inefficient or in-
applicable [46].
In broad terms, inorganic membranes consist of ceramic or carbon-
based membranes [47]. The most used oxides in commercialized ce-
ramic membranes are silica, alumina, titania, and/or the mixtures of
their oxides, and among these zeolite is the most important one [48].
A typical ceramic membrane has an anisotropic structure, which
comes from the progressive deposition of fine particles during fabrica-
tion of the membrane. It consists of a microporous support and mesopo-
rous or microporous active layers [49]. Despite the advantages of
inorganic membranes over polymeric membranes, the difficulties in
handling the preparation of the membrane, the high manufacturing
cost, and the relatively high thickness, which directly affects perfor-
mance have hindered its commercialization.
Recently, a lot of work has been done to prepare low-cost inorganic
membranes by replacing affordable materials such as clay and organic
pore formers to encourage the use of inorganic membranes at a larger
scale [50]. This type of RO membrane can be further developed by ex-
ploring and investigating other materials suitable for fabrication or by
reducing the thickness of the membrane for better performance.
Over the past years, polymeric and ceramic membranes have been
used widely in the desalination industry, and researchers have been
working to combine the advantages of both the membranes to form
one new membrane. This membrane material is called mixed matrix
membranes (MMMs).
Also known as hybrid membrane, MMMs combines the unique fea-
tures of both the polymeric matrix and the inorganic fillers to become a
new, high-performance material. This hybrid organic–inorganic system
enhances the properties of the polymeric matrix by combining the ad-
vantages provided by the added inorganic fillers, which is a promising
means to achieve the desired membrane morphology with excellent se-
lectivity and permeability, and high chemical, mechanical, and thermal
stability over the wide temperature and pH ranges, as well as fouling re-
sistance of the composite membrane [51]. The inorganic fillers can be a
porous and/or nonporous material including zeolite, activated carbon,
carbon molecular sieve, carbon nanotubes, silica, alumina, silver, and/
or titanium oxide nanoparticles. Nevertheless, these advancements
face some difficulties that have restricted their wider application.
These difficulties include the identification of filler material for synthe-
sis, complex fabrication process, high cost, agglomeration, phase separa-
tion, inorganic particle concentration, and fouling [52].
Biological membranes are involved with the development of desali-
nation membranes to attain a higher permeability and better selectivity
through aquaporin proteins [53]. A biological water channel protein or
an aquaporin-based biomimetic membranes can potentially achieve a
higher water permeability compared to existing RO membranes, and
they have excellent water transport characteristics with high permeabil-
ity, while maintaining selectivity. However, most of the biomimetic
membranes do not have enough mechanical strength to withstand the
high hydrostatic pressure required by RO membranes [54]. In addition,
 R.H. Hailemariam et al. / Advances in Colloid and Interface Science 276 (2020) 102100
Fig. 5. Timeline of RO membrane development and modification strategies.
the fabrication process takes a longer time and requires highly special-
ized techniques, making it difficult to scale up for large-scale desalination
[55]. Fig. 5 showed the timeline of RO membrane development and the
major modification types.
4. Strategies to improve PA-TFC RO membrane performance
4.1. Addition of co-solvent organic phase during interfacial polymerization
(CAIP)
Commercial PA-TFC RO membranes are typically synthesized by the
IP method to form a thin polyamide layer. Interfacial polymerization
process involves the impregnation of a porous support layer in two re-
active monomers. The most widely used monomers to synthesize aro-
matic polyamide membrane are MPD in aqueous phase and TMC in
organic phase. However, TFC membranes have low water permeability
under a moderate pressure because of the excessively tight crosslink
network and low free volume of the active layer [56].
The performance of the PA-TFC membrane depends on the chemical
and surface properties of the thin film layer, which are characterized by
surface roughness, surface charge, and hydrophilicity. A broad investi-
gation has been carried out on the development of a loose PA-TFC mem-
brane to prepare a highly permeable membrane without lowering salt
rejection, which meets the application requirement. For the purpose
of enhancing surface hydrophilicity of membrane, most of the research
works focus on improving the immiscibility of organic and aqueous so-
lutions by increasing the monomers' reactivity and decreasing the den-
sities of the membrane layers. Addition of a co-solvent in the aqueous or
organic phase may alter the diffusivity, solubility, or reactivity between
the MPD and the TMC. The addition of co-solvent results in the variation
of morphology, thickness, and network structure of the polyamide thin
layer, which ultimately influences the water permeability and overall
performance. Over the years, several researchers have used different
solvents to enhance the performance of the PA membrane, which are
listed in Table 1.
One of the strategies to achieving high permeate flux is to improve
monomer miscibility by addition of additives in the aqueous phase
[57]. For instance, the addition of alcohol and ether in aqueous phase
is used to prepare a membrane with higher permeability and salt rejec-
tion [58]. PA-TFC membrane prepared by the addition of 20 wt% isopro-
pyl alcohol, showed a performance with 99.7% to 99.8% high salt
7
rejection for NaCl and a flux N1.7 m3/(m2 d) which is about 1.7 fold
higher flux than the commercialized polyamide membrane [59]. Addi-
tion of polar aprotic solvents in the aqueous solution could also enhance
the flux permeability of TFC membrane [57]. Polar aprotic solvents have
dipole moments larger than 2.5D, and they do not react with amines.
Some of the polar aprotic solvents used as additives in the preparation
of high-flux membranes are hexamethyle phosphoramide (HMPA), di-
methyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), and N,N-
dimethylformamide (DMF). Using NMP or DMF in aqueous phase at
the time of polymerization will result in a smoother surface than the
membrane without the addition aprotic solvents [60]. The addition of
DMSO in aqueous phase decreases immiscibility between the two
phases by facilitating the diffusion of MPD in the TMC organic solution.
Among the other polar aprotic solvents, DMSO has been reported to
considerably improve the water flux across the PA-TFC membrane,
while maintaining reasonable salt rejection [61]. The morphological
and molecular nature of the polyamide membrane was modified during
the formation of TFC, and morphological studies show that the surface
area and roughness increased with the concentration of DMSO com-
pared to the TFC membrane without the addition of DMSO [62]. In addi-
tion, the aggregate pore size and number of network pores increase,
greatly intensifying the water flux by approximately five-fold [57].
In another study, addition of HMPA in an aqueous solution was used
to prepare fouling-resistant TFC membrane with improved water per-
meability and good salt rejection. HMPA increases the reaction rate be-
tween MPD and TMC. The study's contact angle result shows that the
membrane surface becomes more hydrophilic with the addition of
HMPA [63]. In the membrane prepared by 3 wt% HMPA addition, the
flux reached 51.67 L/m2 h with salt rejection of 98.27%. The permeate
flux increased by 73%, and the salt rejection loss was b0.21% compared
to the non-additive membrane.
The other modification strategy for synthesis of high-performance
desalination membrane is the addition of co-solvents in an organic
phase during interfacial polymerization, which is known as co-
solvent-assisted interfacial polymerization (CAIP) [64]. The first high-
performance membrane was synthesized with the addition of acetone
(0–5 wt%) in the organic phase by CAIP techniques. As shown in Fig. 6
(A), the addition of acetone in organic phase increases the diffusion
rate of MPD in the hexane phase and creates a narrow, miscible zone
by reducing the solubility difference and interfacial tension between
the two phases. This leads to the formation of a loose layer within the
8 R.H. Hailemariam et al. / Advances in Colloid and Interface Science 276 (2020) 102100
Table 1
Effect of addition of solvent for RO membrane modification: (Type of co-solvent; Experimental condition, and membrane performance).
Type of solvent Experimental
condition
2
Acetone in hexane phase • Area 5.1 cm
• Temperature 25 °C
0, 2, 4, 6, 8, 10 (wt%) • Operation pressure of
1.5 MPa
• NaCl 2000 ppm
• MgSO4 500 ppm
2
Acetone in hexane phase • Area 44 cm
• Temperature 25 °C
0.5, 1, 2, 3, 5 (wt%) • Operation pressure of
1.5 MPa
• pH of 6.5–7.0
• NaCl & MgSO4
2000 ppm
Acetone in hexane phase • Area 5.1 cm2
• Pressure of 1.5 MPa
(0–5%) • temperature of 298 K
• NaCl & MgSO4
2000 ppm
Acetone in hexane phase • Effective area 44 cm2
• Pressure 1.5 MPa
(2 wt%) • pH of 6.5–7.0
• Temperature of 25 °C.
• NaCl 2000 ppm and
IPA 500 ppm
Acetone in heptane • Effective area 42 cm2
organic solvent • Pressure 225 psi
• temperature was 25
(0.5, 1, 2, 3, 4, 5 wt%) °C
• NaCl 2000 ppm
Acetone in n dodecane Area 42 cm2
• •
organic solvent Pressure 1.6 × 106 Pa
• For 3 wt% fast increase in pore size
•
pH of 6.5 ± 0.5
(0.5, 1, 2, 3, 4, 5 wt%) •
temperature was
25 °C
NaCl 2000 ppm
Ethyl acetate • Area 44 cm2
In hexane phase • Temperature 25 °C
• Operation pressure of
0.5, 1, 2, 3, 5 (wt%) 1.5 MPa
• pH of 6.5–7.0
NaCl & MgSO4 2000
(wt%) ppm
Ethyl acetate • Effective area 44 cm2
In hexane phase • Pressure 1.5 MPa
• pH of 6.5–7.0
(2 wt%) • Temperature of 25 °C.
• NaCl 2000 ppm and
IPA 500 ppm
Ethyl acetate n-heptane • Area 42 cm2
mixed with co-solvent • Pressure 225 psi
• pH of 6–7
(0.5, 1, 2, 3, 5 wt%). • temperature at 25 °C
• NaCl 2000 ppm and
MgCl2 and IPA
Ethyl acetate • Area 42 cm2
n-Dodecane (wt%) • Pressure 1.6 × 106 Pa
• pH of 6.5 ± 0.5
• Temperature was 25
°C
NaCl 2000 ppm
Diethyl ether • Area 44 cm2
in hexane phase • Temperature 25 °C
• Operation pressure of
0.5, 1, 2, 3, 5 (wt%) 1.5 MPa
• pH of 6.5–7.0
NaCl and MgSo4
2000 ppm
Structural and morphological Performance Ref.
changes/change on
Permeation Rejection
the intrinsic behavior of membrane
• Smoother surface Flux significantly increased Decreased as acetone [65]
• Thinner layer membrane b8 nm concentration
• Pore size; Increase as acetone increase 2% acetone = 4-fold increase in water
• Increase rate of diffusion of MPD flux For 2% acetone rejection
• Mechanism of membrane formation; N99%
Loose layer formed at first N4% = lower flux
• Narrow reaction zone For acetone ≥4%
significantly decreased
• Large ridges-and-valleys amounts of Drastic increase with acetone N3 wt% significantly [67]
polyamide were formed concertation decreased
• Smooth structure
• Flat or smooth surface morphology At higher acetone concentration flux • No considerable salt [64]
• Thinner dense layer b100 nm increased up to 4 times. From rejection (N95.5%) loss.
• Narrow miscibility zone (1.97 × 10−12 to • For 2–5 wt% rejection
• Loose and thin polymer layer formed at 7.71 × 10−12) decreased from 96 to
the early stage b90%
• Large pore size
• Multi-layered polyamide structure • Permeate flux was significantly • Slightly decreased [68]
formed (100 nm to 10 μm) increased b98% for NaCl
• MPD diffusion rate increased • Highest flux among other co-solvents
• Larger surface area • N higher than 1.0 m3/(m2 d) for NaCl b80% for IPA
• The order of the sizes of the multilayered • N higher than 1.2 m3/(m2 d) for IPA
structure was as follows: acetone N ethyl
acetate N IPA N diethyl ether N toluene.
• Smooth and homogeneous surface and Flux increases as acetone increases Drastically drop at 2% of [70]
larger pore size acetone
• Roughness TFC = 27 and CAIP = 33
• High thermal stability
• Transmission of light is higher
• Contact angle increased as acetone
increase reached peak at 2 wt% and
decreased
Pore size larger than hexane • Increases the flux by ~25%. Hexane Diethyl ether N ethyl [72]
solvent shows that dodecane based acetate N acetone.
• Low thickness and high contact angle membranes yield higher flux for all
• Smaller contact angle in larger and the salts Larger salt rejection than
smaller co-solvent concentrations • Acetone at N3 wt% flux increase hexane based membrane
significantly
• Slight increase in the ridge-and-valley Increase 3 wt% showed 1.8 m3/(m2 d) • Slightly decreased [67]
structures with 1 wt% and multi-layered For 0–3 wt% rejection
polyamide structure with 2 wt% decreased from
• Smooth structure 99.3–99.5% to 99%
• Multi-layered polyamide structure less Permeate flux was significantly • Slightly decreased [68]
than acetone increased b99% for NaCl
• MPD diffusion rate increased
• Larger surface area Highest flux among other co-solvents b90% for IPA
* higher than 1.0 m3/(m2 d) for NaCl
* higher than 1.2 m3/(m2 d) for IPA
• Smooth and homogeneous • High flux (large pore sizes) Decreased slightly [71]
• surfaces of the membranes consisted of
2
continuous ridges and valleys For 5 wt%, 54.23 l/m h
• High thermal stability
• Adsorption of light energy increased,
thicker membrane
Higher contact angle than diethyl ether
• Smaller contact angle in larger and Increases the flux by ~25%. Hexane Diethyl ether N ethyl [72]
smaller co-solvent concentrations solvent shows that dodecane based acetate N acetone.
• Low thickness and high contact angle membranes yield higher flux for all the
salts Greater salt rejection than
hexane based membrane
• Gradual increase in the size of the ordi- • Increase gradually 5 wt% showed slightly decreased [67]
nal ridge-and-valley structures, range 1.2 m3/ (m2 d).
(100 to 500 nm) For 0 to 5 wt% rejection
• highest concentration (5 wt%) required decreased from
to form multi-layered polyamide struc- 99.4–99.6% to 99–99.3%
ture
• Smooth structure
 R.H. Hailemariam et al. / Advances in Colloid and Interface Science 276 (2020) 102100 9

Table 1 (continued)

Type of solvent Experimental Structural and morphological Performance Ref.

condition changes/change on
Permeation Rejection
the intrinsic behavior of membrane

Diethyl ether • Effective area 44 cm2 • Formation of multi-layered polyamide Permeate flux was gradually increased Same rejection with [68]
Hexane phase • Pressure 1.5 MPa structures lesser than acetone and ethyl Nhigher than 0.6 m3/(m2 d) for NaCl membrane with no
• pH of 6.5–7.0 acetate Nhigher than 0.8 m3/(m2 d) for IPA additives
(2 wt%) • Temperature of 25 °C. • MPD diffusion rate increased
• NaCl 2000 ppm and • Larger surface area b99% for NaCl
IPA 500 ppm
b90% for IPA
Diethyl ether in • Area 42 cm2 • Smooth and homogeneous • High flux (large pore sizes) Decreased slightly [71]
n-heptane mixed • Pressure 225 psi • The surfaces of the membranes consisted • for 3 wt% 42.17 l/m2 h
• PH of 6–7 of continuous ridges and valleys
• Temperature at 25 °C • High thermal stability
(0.5, 1, 2, 3, 5 wt%). • NaCl 2000 ppm and • Adsorption of light energy increased,
• Mgcl2 and IPA thicker membrane
Contact angle significantly increased
Diethyl ether • Area 42 cm2 • Smaller contact angle in larger and Increases the flux by ~25%. Hexane Diethyl ether N ethyl [72]
n-Dodecane • Pressure 1.6 × 106 Pa smaller co-solvent concentration solvent shows that dodecane based acetate N acetone.
• pH of 6.5 ± 0.5 • Low thickness and high contact angle membranes yield higher flux for all the
• Temperature was 25 salts Greater salt rejection than
°C hexane-based membrane
NaCl 2000 ppm
Ethyl formate • Area 19.625 cm2 • Multi-layered structures are formed • Increased remarkably • The rejection exceeded [66]
(nanofiltration) • Pressure 1.6 MPa • Narrow miscibility zone 90% when the content
• Temperature was 25 • Surface roughness increased For 4 wt% flux 45 L/m2 h of ethyl formate was
(0, 2, 4, 6, 8, 10 wt%). °C • Smaller pore b4 wt%.
• NaCl and MgSO4 at • The amount of PA increased by addition
2000 ppm of ethyl formate
Contact angle slightly decreased from 71
to 54, hydrophilicity enhanced due to
the rougher surface
Propanone • Area 19.64 cm2 • Thickness slightly decreased for dense Flux is increased from 4.85 (kg/m2h) for • TFC-0 N TFC-B N TFC-P. [69]
• pressure 6.5 bar active layer TFC-0 to 7.7
(1.5 wt%) • Temperature was 25 • Membrane with loose and thin polyam- Rejection 88 ± 0.4
°C ide layer and smoother surface
• NaCl 2000 ppm • Narrow miscibility zone
• High porosity
Smoother surface formed
Butanone • Area 19.64 cm2 • Surface rougher than membrane with Flux is increased from 4.85 (kg/m2h) for • TFC-0 N TFC-B N TFC-P. [69]
• pressure 6.5 bar propanone TFC-0 to 9.97
(1.5 wt%) • Temperature was 25 • Thinner section than propanone added Rejection 90 ± 0.5
°C membrane
• NaCl 2000 ppm • Narrow miscibility zone
• High porosity
Smoother surface formed
Toluene same IP • Effective area 44 cm2 • Same ridge-and-valley structure with Same with membrane with no additives Same with membrane [68]
(2 wt%) • Pressure 1.5 MPa membrane without co-solvent with no additives
• pH of 6.5–7.0
• Temperature of 25 °C.
• NaCl 2000 ppm and
IPA 500 ppm
Isopropyl alcohol (IPA) • Effective area 44 cm2 • Large ridge-and-valley structure High flux Significantly lower [68]
• Pressure 1.5 MPa • holes were observed on the surface rejection
(2 wt%) • pH of 6.5–7.0
• Temperature of 25 °C
NaCl 2000 ppm and IPA
500 ppm
N,N′ – dimethyl • Effective area 44 cm2 • Low miscibility with hexane High flux Significantly lower [68]
formamide (DMF) • Pressure 1.5 MPa rejection
• pH of 6.5–7.0
(2 wt%) • Temperature of 25 °C
• NaCl 2000 ppm and
IPA 500 ppm
Polar aprotic solvents in • Area 17.34 cm2 • Diffusion kinetics; absorbance become For 3% (MH-3) the flux 51.67 L/m2 h For 3% (MH-3) Good salt [63]
aqueous phase • Pressure 1.55 MPa stronger, thicker reaction zone, and rejection of 98.27%.
• Temperature of 25 ± • Polyamide skin layer increase
Hexamethyl 0.1 °C • Contact angle decreased
phosphoramide NaCl 2000 ppm • Average skin layer thickness gradually
increases
(1, 2, 3, and 4 wt%) • Average roughness increased
• Hydrophilicity increased
• Fouling further study needed
Polar aprotic solvents • Pressure of 225 psi • Reducing the immiscibility between • large increase in water flux, up five-- • Salt rejection not [62]
aqueous phase • Temperature of 25 °C aqueous/organic fold compared to FT-30 sacrificed considerably
• NaCl 2000 ppm • Ridge-and-valley structure

(continued on next page)

10 R.H. Hailemariam et al. / Advances in Colloid and Interface Science 276 (2020) 102100

Table 1 (continued)

Type of solvent Experimental Structural and morphological Performance Ref.

condition changes/change on
Permeation Rejection
the intrinsic behavior of membrane

Dimethyl sulfoxide • Peak-to-valley distance increased

(DMSO)
1.0, 2.0, 3.0, and 4.0 wt%,
Polar aprotic solvents in
aqueous phase
Dimethyl sulfoxide
(DMSO)
1.0, 2.0, and 3 wt%
• Increase mean height, surface roughness, Flux in gfd Rejection in %
and surface area For 1 wt% = 49.2 For 1 wt% = 95.2
• Cross-linked amide linkages increase For 2 wt% = 51.4 For 2 wt% = 93.1
For 3 wt% = 68.7 For 3 wt% = 89.6
For 4 wt% = 76.9 For 4 wt% = 87.4
• Pressure of 225 psi • Surface roughness and surface area • large increase in water flux, up to • Reduced with increasing [57]
• Temperature of 25 °C increase 5-fold DMSO
• NaCl 2000 ppm • Considerable increase in the crosslinked
amide linkages Flux in L/m2h
• Membrane show two types of pores— For 1 wt% = 79.5 Rejection in %
network pore and aggregate pore. For 2 wt% = 87.4 For 1 wt% = 96.4
For 3 wt% = 116.8 For 2 wt% = 95.1
For 3 wt% = 89.6

zone and, gradually, after a short period of time, a thin dense layer is
formed as shown in Fig. 6(B) [65]. Compared with the conventional IP
process, in CAIP, a membrane with a thin layer and flat morphology is
formed. Furthermore, the result in Fig. 7 indicates the membrane pre-
pared with 2 wt% of acetone exhibits approximately four-times higher
permeate flux without considerable loss of salt rejection when com-
pared with the PA membrane prepared without acetone.
Ethyl formate (C3H6O2) is used as a co-solvent to enhance the flux
performance of polyamide composite membrane [66]. The prepared
membrane forms a narrow miscibility zone between the two solutions,
which leads to the formation of a thicker reaction zone. The thicker
zone, along with the lower content of MPD solution, leads to the forma-
tion of a multi-layered loose polyamide structure. The prepared mem-
brane has a more hydrophilic surface, which causes the permeate flux
to increase more than twice (from 23 to 45 L/m2 h) the commercial
TFC membrane, while the salt rejection remains at a high level (N90%).
However, after a long-term test on the CAIP membrane with 4 wt% of
ethyl formate, the water flux showed a slight decline due to the multi-
layered, loose PA layer formation. The TFC membrane synthesized
with ethyl formate could be used in brackish water reverse osmosis
(BWRO) for production of potable water and its suitable to use in low
pressure driven membrane systems.
Different co-solvents have been utilized for the synthesis of mem-
brane with controlled surface morphology. In CAIP process, co-
solvents (acetone, diethyl ether, ethyl acetate, isopropyl alcohol (IPA),
toluene and N,N′-dimethyl formamide (DMF)) are added to the organic
hexane phase to control the surface morphology and polyamide
network structure [67,68]. The addition of DMF and IPA as co-solvents
reveals a whitish layer, which leads to a formation of a milky hexane
phase. The Hildebrand solubility parameters for DMF and IPA were far
from the hexane phase and close to the water phase; thus, they have
lower miscibility with hexane than the other co-solvents, and are
found to be unsuitable for layer formation. A membrane with IPA sol-
vent exhibited a large ridge-and-valley structure because the formed
polyamide layer is not continuous and holes were observed on the sur-
face of layer. This may be a result of lower miscibility between the IPA
and hexane solutions, and unbalanced reactivity and diffusion rate
among the MPD molecules in the TMC solution. Moreover, a membrane
with the addition of DMF and IPA demonstrated significantly lower re-
jection and higher flux than the membrane with no addition of DMF
or IPA. On the other hand, the addition of toluene resulted in a similar
ordinal ridge-and-valley structure and performance with the mem-
brane without the addition of solvent, because n-hexane and toluene
belong to the same hydrocarbon group. Surface morphology with addi-
tion of acetone, ethyl acetate, and diethyl ether exhibited a multi-
layered polyamide structure. Based on the size of the multi-layer struc-
ture formation, the order of compounds is as follows: -acetone N ethyl
acetate N IPA N diethyl ether N toluene.
The permeate flux was significantly increased by the addition of co-
solvents in the hexane solution. Among the membranes prepared by
CAIP, the membrane synthesis by addition of 3 wt% ethyl acetate
showed better performance with a rejection rate of N99% and a perme-
ate flux rate of 1.8 m3/(m2d), which is more than three times that of the
membrane prepared without a co-solvent, and for 1 wt% acetone and

Fig. 6. Scheme for (A) MPD diffusion in TMC with and without acetone as a co-solvent, and (B) formation of polyamide structure in IP and CAIP membranes [65].
 R.H. Hailemariam et al. / Advances in Colloid and Interface Science 276 (2020) 102100 11

Fig. 8. Types of solvent used for co-solvent-assisted interfacial polymerization process.

is 136.8 LMH due to the increased membrane surface porosity. Com-

pared to the conventional RO membrane, the membrane with ethyl ac-
etate (for all concentrations) exhibited a high flux while maintaining a
rejection N90%. For instance, for 3% ethyl acetate, the values of average
flux and rejection were 59.25 LMH and 97.7%, respectively. Diethyl
ether in all concentrations (0.5 to 5) showed the best performance in
terms of both flux and rejection. For 5% diethyl ether, the average flux
Fig. 7. Permeation and salt rejection for the two types of membrane. (A1: traditional
membrane prepared by conventional IP, B1: CAIP membrane) [64]. and salt rejection values were 63 LMH and 97.65%, respectively. Gener-
ally, CAIP membrane performance depends on the type and concentra-
tion of co-solvent used.
5 wt% diethyl ether addition, the recorded water fluxes were
1.0 m3/(m2d) and 1.2 m3/(m2d), respectively [67]. 4.2. RO membrane surface modification
The impact of ketone co-solvent (propanone and butanone) in the
CAIP procedure studied for lactose recovery purpose [69], the structural Significant research has been carried out on RO membranes to en-
and physiochemical properties and performance of nanoporous TFC mem- hance its water permeability and salt rejection, and to give it antifouling
brane was also investigated. The SEM and AFM images captured during the and chlorine resistance by optimizing the chemistry and structure of the
study indicated the formation of a less crosslinked structure with smooth membrane layer. The surface modification of PA-TFC RO membrane is
and large average pore size. Moreover, the membrane prepared with one of the major methods to increase membrane performance through
propanone and butanone showed a significantly increased flux, whereas modification of substrate, monomers, and addition of additives to
lactose and NaCl rejection did not show any remarkable loss.
The effects of addition of acetone co-solvent in non-polar heptane
organic phase instead of hexane was also investigated [70]. High contact
angles were observed as the acetone concentration increased, and high
permeate fluxes were observed with relatively low salt rejection. Hep-
tane has a molecule of larger C\\C chain than that of hexane [71]. The
addition of ethyl acetate and diethyl ether in non-polar heptane phase
resulted in good performance. The synthesized membrane consists of
ordinal and large ridge-and-valley formations. The addition of solvent
reduced surface roughness properties. In addition, a thermal gravimet-
ric analysis indicated that the membranes exhibited high thermal stabil-
ity under a degradation temperature.
In another research, three co-solvents (acetone, ethyl acetate, and
diethyl ether) were added by interfacial polymerization in a dodecane
solvent [72]. The result showed that the use of dodecane solvent helped
the membrane show better performance than hexane-based mem-
branes. The recorded pore size of dodecane membrane is larger than
that of hexane, because the former has a larger molecular volume.
Therefore, the molecular volume of the co-solvent played a role in de-
termining the pore size of the membrane, i.e., greater the molecular vol-
ume, larger the pore size.
Generally, by adding solvents during the interfacial polymerization
process, it is possible to synthesize membrane with desirable surface
properties and improved performance. Examples of co-solvents used
in interfacial polymerization are shown in Fig. 8.
The effects of utilizing various types of generic co-solvents (acetone,
ethyl acetate, and diethyl ether) and their corresponding ranges, and
the mean value of flux and rejection of CAIP membrane from different
literature listed in Table 1, are summarized in Figs. 9, 10, and 11. Gener-
ally, the addition of acetone in small concentrations has a significant
impact on both rejection and flux performance. For 3% acetone addition,
the average experimental flux and rejection values are 65.5 LMH and
89%, respectively. However, at higher concentrations (5%) of acetone, Fig. 9. The range and mean value of flux and rejection for different acetone concentrations
salt rejection is greatly decreased to 8.6%, while the average water flux [Source: [64,65,67,68,70,72]].
12 R.H. Hailemariam et al. / Advances in Colloid and Interface Science 276 (2020) 102100
Fig. 10. The range and mean value of flux and rejection for different ethyl acetate
concentrations [Source: [67,68,71,72]].
improve chemical resistance, control pore size, elimination of defects,
and improved biofouling resistance. Physicochemical properties of com-
posite RO membrane, such as physical morphology, interfacial proper-
ties, chemical structure, permeability, and rejection performance,
depend on chemical structure of membrane support materials, polymer
concentration, monomer structure, added solvents and catalysts, reac-
tion and curing temperature and other post-treatment procedures [73].
The PA-TFC membrane performance depend on the surface proper-
ties of the membrane such as hydrophilicity, surface roughness, and sur-
face charge. Higher hydrophilicity promotes enhanced wettability,
which results in higher permeability, as well as better fouling resistance
for the membrane surface [74]. However, hydrophilicity of a PA-TFC
membrane is not sufficient due to the highly crosslinked network;
hence, enhancing the surface hydrophilicity is important. The surface
charge of the membrane depends not only on fouling but also on the
charge of foulant, considering the membrane's electrostatic charge is es-
sential for the reduction of membrane fouling. When the membrane
surface has a similar charge as the foulant, the electrostatic repulsion
force between the two surfaces prevent fouling deposition on the mem-
brane surface [75].
Surface roughness has a strong effect on the performance of the
membrane and has a direct relation with the membrane flux. Higher
surface roughness results in a higher surface area, which provides better
wettability and contributes to a higher permeate flux [58]. Nevertheless,
surface roughness is directly related to membrane fouling in that mem-
branes with rougher surfaces are highly susceptible to fouling. In gen-
eral, membranes with high hydrophilicity, smoother surface, and low
negative charge demonstrated better fouling resistance [74].
4.2.1. Modification of support layer of PA membrane
The porous support layer of PA-TFC RO membrane gives mechanical
strength to the thin selective active layer for resistance against higher
Fig. 11. The range and mean value of flux and rejection for different diethyl ether
concentrations [Source: [67,68,71,72]].
hydraulic pressures applied throughout the process. Experimental and
modeling results indicate the significance of selecting a suitable support
layer on the performance of permeate flux and salt rejection. The nature
of the support layer co-defines the interface where IP occurs, and fine-
tuning of support layers through modification is essential to form a
defect-free PA layer [76].
Membrane porous support structures are prepared from different
polymers, such as polysulfone (PSU), polyethersulfone (PES), polyphen-
ylene oxides (PPO), polycarbonate (PO), poly (phthalazinone ether sul-
fone ketone) (PPESK), polyacrylonitrile (PAN), polypropylene (PP),
polyetherimide (PEI) and others using phase inversion techniques
[77]. However, the most widely used polymer for fabricating composite
RO membranes is PSU, as it is cheaper, widely available, compatible with
IP, stable against thermal, chemical, and bacterial attacks, and tolerant
to a wide range of pH [78]. Expanding the selection of support and
using modification are expected to enhance chlorine resistance [79],
to give antifouling property [80] and improve the performance of PA-
TFC RO membranes.
Factors influencing the properties of support layer and the perfor-
mance of TFC membrane include polymer concentration, temperature,
air humidity, and types of solvent and additives during the fabrication
process [73]. In addition to morphology, the support layer's chemical
property has a large influence on the formation of ultrathin active PA
layer, which may cause variations in membrane permeability and rejec-
tion, while affecting the propensity of scaling and fouling. A highly hy-
drophobic and porous support caused the formation of a rougher,
more permeable membrane; whereas, hydrophilic supports caused
the formation of a smooth and thinner PA composite membrane with
low permeability [73]. The influence of support-layer porosity on mem-
brane performance has been studied by [81], and the result revealed
that the active layer formed on low-porosity supports have low surface
porosity, lower thickness, lower crosslinking, and weak bonding with
 R.H. Hailemariam et al. / Advances in Colloid and Interface Science 276 (2020) 102100
the support. Contrary to this, on highly porous support layers, the active
layers exhibited high crosslinking, greater thickness, and strong bond-
ing with the support, and it was found that the support layer with
high concentration of PSU showed a higher water permeability and con-
tact angle.
The generation of a functional group on the surface of a support layer
might form a covalent bond between the active layer and the support
layer, which may lead to the formation of a TFC membrane with high
salt rejection performance and structural stability [82]. Modification
by the addition of organic solvents in the PSU casting solution results
in the variation of physical and chemical properties of the PSU support
[73,83]. For instance, the substrate fabricated with the addition of hy-
drophilic additives such as polyvinyl pyrrolidone and polyethylene gly-
col in a precipitation bath promotes a more hydrophilic character to the
support layer, because of the presence of hydroxyl, ether, or secondary
amide groups in the additives. The prepared membrane was a thinner,
smoother, and less permeable polyamide layer than the membrane
with no additives. The MPD diffusion in the substrate was limited be-
cause of the hydrogen bond between MPD and the additives inside
the pore, and the organic solvent addition increased the effective layer
thickness for water permeation [73]. The support layer synthesized by
the addition of organic solvents, such as n-methyl pyrrolidone, showed
higher porosity than the other solvents.
The other support layer modification method is plasma treatment
with hydrophilic monomers. This method is used to improve the sup-
port layer hydrophilic properties and change the film structures
[78,84,85]. Low-temperature plasma treatment of membrane supports
was conducted for investigation of TFC RO membrane performance
[84]. The treated PSU support exhibited improved chlorine resistance
with slightly improved water flux and salt rejection than the conven-
tional PA-TFC membrane. Moreover, due to the enhanced adhesion
properties between the support layer and the active layer, a better inter-
facial polymerized layer could be formed on the modified support.
In the recent years, the support layer modified by hydrophilic in-
organic particles such as MWNTs, zeolites nanoparticles, amorphous
non-porous silica, and titanium dioxide (TiO2) for improvement of
TFC membrane performance [86]. Compared to pure PSU support,
nanocomposite RO membranes by incorporation of zeolite or silica
shows higher initial permeability with increased salt rejection. Nano-
composite-supported RO membranes are one of the potential re-
search approaches for the mitigation of irreversible internal fouling
that comes with membrane compaction, which helps to enhance
the mechanical stability of the membrane for applications in seawa-
ter and brackish water desalination [87]. The addition of zeolite in
the wet-phase inversion method helped form smoother hydrophilic
membrane surfaces to increase water permeability and rejection.
Moreover, it increased the stability of the membrane under high
physical compaction [86].
Fig. 12. Schematic illustration of (a) conventional interfacial polymerization (IP) and (b) support-free IP (SFIP) for the fabrication of TFC membranes [88].
13
Recently, support-free IP (SFIP) approach was used to synthesize PA-
TFC membrane. Unlike in the conventional IP in the SFIP method, the PA
layer in the PA-TFC membrane formed separately and latched on to the
support layer. A polyacrylonitrile (PAN) support layer was treated with
hydrolysis to tune its chemical structure, and nitrile (-CN) groups of
PAN converts into carboxyl (–COOH) groups. SFIP is used to fabricate a
smooth and thin polyamide structure with a highly wettable and nega-
tively charged surface as it involves uniform amine diffusion during film
formation Fig. 12 [88].
Recently, acid treatment of PSU support layer was used to increase
the performance of the membrane [89] [90]. A metal–organic frame-
work (MOF) treated with sulfuric acid used to modify the membrane
[89]. The addition of hydrophilic acid–MOF groups and the strong
bonding between the cluster and copper ions enhanced the porosity
and hydrophilicity of the membrane. The prepared membrane reveals
a thinner section with improved permeability and enhanced fouling
resistance. In other research, a combination of sulfuric acid-treated
PSU support and thin-film nanocomposite (TFN) membranes with
a-MWCNT-TNT showed a high permeability and rejection [90].
The PSU and sulfonated PSU porous-UF supports were blended for
enhancement of RO membrane performance [91]. Recently,
Sulfochlorinated polysulfone (SC-PSf) membrane was synthesized by
metalation sulfochlorination of PSU to increase the chlorine resistance
performance. The modified membrane showed a long-term stability
against chlorine [79]. In Table 2, modification of PA-TFC RO membrane
support layer, experimental condition, purpose, and performance are
listed.
4.2.2. Modification of active layer
Modification of polyamide thin layer using different methods
could significantly affect membrane performance. The active layer
of PA-TFC RO membrane is made of a crosslinked aromatic PA syn-
thesized by interfacial polymerization between amines and aromatic
acyl chlorides. The most commonly used monomers are MPD and
TMC [92]. When PA membrane is immersed into an aqueous solu-
tion, it possesses amino- and intrinsic carboxylic groups on the sur-
face due to the incomplete crosslinking of the polymer, and it has
been proved that there are many negatively charged functional
groups on the membrane surface. Physical morphology, structure,
and chemistry of the active layer have a direct effect on membrane
hydrophilicity, permeability, selectivity, surface roughness, and
fouling resistance of the RO membrane [93]. Interfacial parameters
including concentration and types of monomers, addition of
additives, solvent viscosity, condition of polymerization and curing
temperature, and processing time need to be optimized to synthe-
size high-performance TFC membranes [43,67,94]. Controlling
the surface properties of a PA active layer through surface
modification was one of the promising methods for preparation of
14 R.H. Hailemariam et al. / Advances in Colloid and Interface Science 276 (2020) 102100

Table 2
Modification of RO membranes support layer in recent years; support layers, experiment condition, purpose, and performance.

Support layer Experimental Modification mechanism Performance after modification Ref

condition

Polysulfone Temperature = 25 °C Conventional phase-inversion method Enhanced chlorine resistance [84]

Polypropylene
Polyvinylidene fluoride
Polysulfone
Polysulfone
Polyacrylonitrile
(PAN and HPAN) support
MOF/PSU support layer
PSU support
layer/microstructure
(HPμS) support
Membranes
Polysulfone support with
thin-film nanocomposite
(TFN) membrane
Polysulfone/sulfonated PsF/SPSf
blended support
sulfochlorinated polysulfone
(SC-PSf)
PSF-CNF-Ag ex situ
Effective surface Enhanced adhesion between two layers
Area = 13.85 cm2 Plasma treatment with monomers used Water flux 0.5–1.1 (l/m2 atm h)
Pressure = 30 bar Rejection 94–98%
NaCl 2000 ppm Membranes treated with AA and AM
showed better performance
Temp = 25 °C Plasma treatment with monomers used AN, AA, ED, AM, or PAMb Chlorine resistance enhanced [84]
Effective surface Area = to hydrophilize the support Enhanced adhesion between two layers
13.85 cm2 Water flux 0.2–1.0 (l/m2 atm h)
Pressure = 30 bar Rejection 50–97.0%
NaCl 2000 ppm
Temperature = 23 ± 1 Plasma treatment by using oxygen, methane or gas mixture Contact angle reduced 119 to 52° [78]
°C Salt rejection: 2–99% (2000 ppm NaCl
NaCl 2000 ppm solution;
Pressure from 10 to 30 P = 300 psi; T = 25 °C);
psi. Pure water permeability 0.55–0.25
Lm−2h psi
Temperature = 23 ± 1 Plasma treatment by using oxygen, methane or gas mixture Contact angle reduced from 80 to 29° [78]
°C (1:1 ratio mixture) Salt rejection: 79%–95% (2000 ppm NaCl
NaCl 2000 ppm solution;
Pressures from 10 to 50 300 psi; 25 °C);
psi Pure water permeability (0.15–0.24 L m2
h psi).
Temperature of 25 °C Nonsolvent-induced phase separation (immersion precipitation) Salt rejection: 83–94% [73]
Pressures 225 psi Addition of NMP in precipitation water bath, or organic water flux: 32.8–6.5 L m−2 h
NaCl 2000 ppm additives, PEG or PVP
Effective area = 14.5 Support-free interfacial polymerization (SFIP) Contact angle decreased [88]
cm2 PAN support hydrolyzed by soaking in NaOH solution Increased negative charge
Temperature of 25 °C Water flux 13.3 ± 0.8 L m−2 h−1
Pressure of 15.5 bar Salt rejection 99.0 ± 0.3(%)
NaCl = 2000 ppm
Effective area = 27.01 Phase inversion in an Porosity of the membrane increased [89]
cm2 MOF-PSU / DMF / water system Thinner polyamide formed thickness
Feed temperature: 25 °C (0.029)
Feed pressure: 250 psi To increase hydrophilicity and structural stability of MOFs, OH Low roughness enhanced water flux and
NaCl = 2000 ppm and SO4 groups, formed by sulfonating HKUST-1 with acid, were fouling resistance
introduced Water flux 28 LMH
Rejection 96%
Effective area = 42 cm2 Non-solvent induced phase separation (NIPS) with varying (N1D7) support DMF with respect to [83]
NaCl = 2000 ppm ration of NMP and DMF NMP0.875
Pressure = 15.5 bar Water flux = 4.68 (±0.33) Lm−2 h−1
bar−1
Salt rejection = 98.3(±0.1) %
Temperature = 25 °C Acid treated with sulfuric acid (H2SO4) Contact angle (64.25 ± 6.61)° [90]
Effective filtration area Water permeability at 0.87–1.13 L/m2.h.
of 14.6 cm2 bar
Pressure of 15 bar NaCl rejection 97.11–97.69%
Effective area of 12 cm2 SPSf was used to modify the conventional PSU UF. Higher porosity [91]
NaCl = 2000 ppm Non-solvent –induced phase separation Bigger pore diameter
Pressure of 1.55 MPa Smoother and more hydrophilic surface
Higher water flux of approximately 1.2
times greater than the conventional
membrane
Effective area of 15.79 Metalation sulfochlorination of polysulfone (PSf) and TFC was Water flux 17.8 LMH and NaCl rejection [79]
cm2 prepared by coating method 96.9%
NaCl = 2000 ppm Long-term stability against chlorine
Pressure of 1.55 MPa
Effective area of 15.79 polysulfone membranes modified with carboxyl functional Gram-positive bacteria showed higher
cm2 groups (CNFCOOH) and silver nanoparticles(AgNPs) sensitivity for PSF-CNF-Ag (solid phase) [80]
NaCl = 2000 ppm Gram-negative species showed
Pressure of 1.55 MPa sensitivity of PSF-CNF-Ag (liquid phase)

Recommended to use for wastewater

treatment

high-performance membranes. Some of the approaches involve the
reduction of surface roughness, construction of super hydrophilic
surface layers, introduction of antibacterial layers, utilization of the
steric repulsion effect, and improvement of the electrostatic surface
charge. In general, modification of the active layer helps enhance
membrane performance and provides chlorine and fouling resis-
tance to the membrane. Depending on the membrane surface and
applied modifying reagent, surface modification is broadly catego-
rized into physical and chemical modifications [95].
4.2.2.1. Physical surface modification. In physical surface modification, the
PA layer and the modifying material are bound by weaker bonds such as
the van der Waals attraction or hydrogen bonds through methods in-
cluding surface coating and surface adsorption [96]. Surface adsorption
 R.H. Hailemariam et al. / Advances in Colloid and Interface Science 276 (2020) 102100
modifies the membrane surface without altering the chemical proper-
ties of polyamide membrane and is carried out using different com-
pounds, for instance, surfactants [74] and charged polyelectrolyte [97].
A homologous series of polyethylene oxide surfactants used for the
surface modification of PA RO membrane with oxides such as polypro-
pylene and octylphenol [98]. This strategy aims to increase the surface
hydrophilicity of the membrane and the steric hindrance of a variety
of nonionic surfactants through the adsorption process. Compared
with the conventional membrane, the modified membrane decreased
in surface roughness while its zeta potential remained the same, en-
hancing the membrane's antifouling property. The membrane was
modified by an anionic surfactant, sodium dodecyl, which increased
the water flux to approximately 142% after the membrane was exposed
to 2000 mg/L of sodium hypochlorite followed by sodium dodecyl sul-
fate [99]. Charged polyelectrolytes have been used in surface adsorption
processes to modify the PA-TFC membrane [97]. The polyethyleneimine
molecules were electrostatically self-assembled on the membrane sur-
face, and the modified membrane exhibited higher surface hydrophilic-
ity and a significant improvement in fouling resistance toward cationic
foulants due to the increased electrostatic repulsion.
The other mostly used physical modification method for PA-TFC RO
membrane is surface coating. In the surface-coating process, a selective
PA layer is immersed into the coating solution, and the remaining sol-
vent is evaporated from the membrane surface at a moderate tempera-
ture to solidify the coating solution for the formation of a thin coating
layer on the membrane surface [100]. Coating material and coating con-
ditions are essential in determining the physicochemical properties of a
coated membrane surface [100]. The most widely used surface coating
material is the hydrophilic polymer containing carboxyl, hydroxyl, en-
zyme, or amino groups [101]. Addition of this type of coating layer
used to promote antifouling property to the membrane by enhancing
surface hydrophilicity, reducing surface charge and roughness without
affecting the rejection and flux performance.
However, in some cases, an additional coating layer increased the
thickness of the membrane, thus giving additional resistance to water
permeability, which may lead to a reduction in the water flux. In addi-
tion to that, because of the weaker interaction between the membrane
surface and the coated layer, in the long-term operation, the coating
material may wash-off due to chemical cleaning processes, which may
lead to the deterioration of the membrane's antifouling property [102].
Surface coating of membrane surface using a hydrophilic polymer
was investigated by several researchers. For instance, poly(ethylene
glycol) (PEG) and PEG-based polymers are the most commonly used
as coating material to enhance the hydrophilic properties of the mem-
brane, to increase antifouling resistance [103].
PEG-based polymers are a good candidate for antifouling coating
layer because of their larger exclusion volume, long-chain flexibility,
and unique coordination with the surrounding water molecules in an
aqueous solution. The membrane behavior after coating by using a se-
ries of crosslinked PEG-base hydrogels with crosslinkers (poly(ethylene
glycol) diacrylate) and co-monomers (poly(ethylene glycol) acrylate,
acrylic acid, or 2-hydroxyethyl acrylate) were investigated by [104],
which found that salt rejection for both uncoated and coated membrane
was N99.0%, and the coated membrane appeared to have increased salt
rejection, while slightly reducing the water flux compared the uncoated
membrane.
Poly(ethylene glycol) acrylate (PEGA)-coated membrane synthe-
sized by a dip-coating method and crosslinked by a glutaraldehyde
(GA) solution to improve the coating layer durability and to enhance
the antifouling property of the RO membrane [105]. The coated
membrane reduced in surface roughness, increased in hydrophilic-
ity, and performed better than the uncoated membrane. In addition,
the modified membrane exhibited a large fouling resistance and re-
covered almost its entire initial filtration performance after the
physical cleaning.
15
The membrane was modified using thermos-responsive copolymers
poly(N-isopropylacrylamide-co-acrylamide) (P(NIPAM-co-Am)), to
improve its surface properties [106]. The result showed that the copol-
ymer (P (NIPAM-co-Am) could be effectively layered on the surface of
the membrane using the dip-coating method. The modified membrane
exhibited the same salt rejection as the original membranes, while the
water permeability depended on the composition of the coating layer
and coating solution concentration. In addition to that, after a long-
term test, the modified membrane was found to possess higher durabil-
ity and performance stability.
Dendrimer based coating used for the modification of RO membrane
[107], the membrane coated by in situ crosslinking of amine functional
polyamidoamine (PAMAM) dendrimers and PAMAM–polyethylene
glycol (PAMAM–PEG) multi-arm stars with difunctional PEG crosslin-
kers. The contact angle of the coated membrane was significantly re-
duced without affecting salt rejection. The reduction in contact angle
indicated more hydrophilic membrane surface with the increased
fouling resistance. To increase the membrane antifouling properties
different advanced chemical used as a coating agent which includes p
(4-VP-co-EGDA), HEMA, HEMA-co-PFDA, HPOEM or PEI coating
followed by GA, hydrophobic PFDA, sericin, polyvinyl alcohol (PVA)
and others [108–110].
Physical surface modification for improving the membrane flux in-
vestigated by different research [111]. Ethanol-soaked polyether–
polyamide block copolymers (PEBAX) were used to coat the membrane,
to improve water flux. Pre-soaking significantly increased the water flux
by wetting of microscopic, disrupting interchain hydrogen bonds and
swelling of the polymer layer. In another research, a membrane surface
treated by chlorine followed by electrostatic deposition of chitosan was
used to improve flux [112]. The membrane showed a charge reversal
in the commercial RO membrane by creating a positively charged
membrane surface, and eventually increasing water permeability and
salt rejection.
To improve chlorine resistance and acid stability of the RO mem-
brane, hydrophilic copolymers poly(N-isopropylacrylamide-co-acryl-
amide) were coated on the membrane surface [113]. The modified
membrane showed good chlorine stability after two months of expo-
sure to hypochlorite (3000 ppm) and HCl (0.5 mol/L) without undergo-
ing any change in membrane performance. In the other study, after IP of
TFC membrane takes places, sorbitol polyglycidyl ether (SPGE) used to
protect the chlorine–sensitive sites on PA membrane surface [24].
A membrane coated with poly(methylacryloxyethyldimethyl benzyl
ammonium chloride-r-acrylamide-r-2-hydroxyethyl methacrylate) (P
(MDBAC-r-Am-r-HEMA)) via free-radical polymerization was used to
improve its antifouling and chlorine-resistance properties [106]. The
coated membrane could tolerate 7–10 times of chlorine exposure than
the uncoated membrane, and the antimicrobial and antifouling mem-
brane properties improved. In another research, to increase the chlorine
tolerance of PA-TFC membrane, a random terpolymer of 2-acrylamido-
2-methyl propane sulfonic acid, acrylamide, and 1-vinylimidazole (P
(AMPS-co-Am-co-VI)) were used, which exhibited better chlorine resis-
tance than the conventional membrane [100]. Recently, membranes
with high chlorine resistance and salt rejection synthesized via coating
of achipolyethylene glycol diacrylate (PEGDA) into the TFC RO mem-
brane [114]. Different physical surface modifications of PA-TFC RO
membrane, and the corresponding membrane type, experimental con-
dition, and performance are summarized in Table 3.
4.2.2.2. Chemical surface modification. In chemical surface modification,
the modifying chemical is bound to the surface of active layer by strong
covalent bonds, which have better structural and chemical stability
[124]. There are different forms of chemical surface modifications,
such as chemical coupling, grafting, hydrophilization, sol-gel coating,
free-radical graft polymerization, atom transfer radical polymerization,
nanoparticle incorporation, and supramolecular assembly [4,96].
16 R.H. Hailemariam et al. / Advances in Colloid and Interface Science 276 (2020) 102100

Table 3
Physical modification of the active layer of RO membrane in recent years; membrane type, experiment condition, purpose and performance.

Commercial Temperature = 25 °C To improve antifouling Dip- coating by sericin followed by GA and • Surface hydrophilicity increased [108]
PA-TFC Pressure = 5.0 bar property H2SO4 crosslinking • Surface negative charge increase with increasing
membrane PH = 6.8 sericin, smoothed surface morphology
(Hangzhou) Effective membrane Sericin = 50–200 mg/L • Improved fouling resistance
area = 19.0 cm2 GA = 0.2% (w/w) • Lower pure water permeability, improved salt
NaCl concentration = H2SO4 = 0.1% (w/w) rejection
500 mg/L
Commercial Temperature = 23 °C To improve antifouling Polyvinyl alcohol (PVA), • Coating thickness varied from 80 to 250 nm [109]
PA-TFC Pressure = 27.6 bar property polyhexamethylene guanidine • Smoother membrane surface (uncoated
membrane Effective membrane hydrochloride (PHMG) membrane = 67.8 nm, PVA coated = 42.5 nm,
LE-400 area = 19.0 cm2 PHMG coated = 53.4 nm and PVA–PHMG =
NaCl concentration = PVA:PHMG ratios 95:5 and 99:1 with a total 57.5 nm)
10 mM polymer content of 2 wt%, applied by • Contact angle decreased for all coatings
dispersion coating method • Surface energy increased for all coatings
• PVA–PHMG-coated membranes maintain high
antimicrobial performance without sacrificing RO
membrane performance
• Reduced water permeability
• Slight increase in salt rejection
Commercial Temperature = 25 °C To improve antifouling Polydopamine (PDA) • Contact angle unchanged [111]
PA-TFC Pressure = 10.3 bar property and increase • With increased dopamine water flux and salt
membrane Effective membrane membrane performance Dopamine solutions prepared dopamine rejection decreased in time
area = 14.6 cm2 hydrochloride in (0.1, 0.5, 2, 4, and 8 • Modified membrane significantly more resistant
XLE RO NaCl concentration = mg/mL) concentration in 15 mM Tris–HCl to fouling
2000 ppm buffer
Commercial Temperature = 25 °C To improve antifouling Hydroxyethylmethacrylate(HEMA) and • With increased PFA content, increased contact [115]
PA-TFC Pressure = 4825 kPa property perfluorodecylacrylate (PFA) angle and roughness
membrane NaCl concentration = • The increased thickness of coating leads to
0.2 M PFA content: 0, 20, 40 increased roughness and decreased water perme-
TFC-HR ability
• Cell attachment significantly reduced with coated
membrane
Commercial Temperature = 25 °C To improve antifouling Poly[2-methacryloyloxyethyl • Contact angle reduced to 18.6 [116]
PA-TFC Pressure = 0.75 MPa property phosphorylcholine • Membrane surface charge changes to neutral
membrane NaCl concentration = (MPC)-co-2-aminoethylmethacrylate • high bacterial adhesion resistance
0.2 M (AEMA)] (P(MPC-co-AEMA)) • Water flux increase by 20%
ES20 RO Salt rejection increased from 94.7 to 96.9%
P(MPC-co-AEMA): 0.1 wt%
Commercial PA Temperature = 25 °C To enhance the Polydopamine (PDA) coating followed by • No change of surface hydrophilicity with modifi- [117]
layer Pressure = 0.75 MPa durability and covalently cation of PDA or PZ
membrane Effective membrane antibiofouling potential immobilization (MPC-co-AEMA) as the • Membrane surface charge changes to neutral by
area = 7.5 × 10−4 m2 of a PZ-immobilized polyzwitterions (PZ) PZ immobilization
ES-20 RO NaCl aqueous solution membrane • Modification did not affect water flux and rejec-
0.05 wt% Dopamine solutions prepared by dissolving tion
0.5 kg/m3 of the dopamine hydrochloride in • Biofouling resistance improved
15 mM Tris–HCl buffer. • With PZ, lower bacterial attachment was
demonstrated
Commercial RO Temperature = 21 °C To improve antifouling Poly(4-vinylpyridine-co-ethylene glycol • Zwitterionic coatings reduce Contact angle (from [118]
membranes Pressure = 300 psi property diacrylate) (p(4-VP-co-EGDA)) deposition 60.4 to 29 °C)
NaCl concentration = followed by • Improved resistance against bacterial adhesion
TFC-HR 2000 mg/L reaction with poly(carboxybetaine acrylic • Reduction in water permeability (approximately
acetate) (pCBAA) units by a quaternization 17%)
reaction with 3-bromopropionic acid • Increase in salt rejection (about 2%)
(3-BPA)
Commercial Temperature = 25 °C To improve antifouling Hydroxyl poly(oxyethylene) methacrylate • Surface roughness decreased slightly [119]
(TFC) SWRO Pressure = 400 or property HPOEM or polyethyeleneimine PEI coating • Less negative membrane with HPOEM coating
membrane 800 psi followed by GA crosslinking, and after that and PEI coating made it more neutral,
NaCl concentration = dipped into aqueous • Contact angle increased for HPOEM and
SHN 2000 or 32,000 ppm bromoacetic acid to obtain carboxylated PEI decreased for PEI coating
(Toray) with 70 ppm coating. • HPOEM coating have better fouling resistance
CaCl2 under BW feed and PEI coating improved fouling
HPOEM or PEI: 0.1 wt%, resistance in SW feed
GA: 0.01 wt%,
Bromoacetic acid: 0.1 wt%
Commercial PA Temperature = 23 °C To improved chlorine Terpolymer of 2-acrylamido-2-methyl • With increased concentration of coating material [100]
TFC Pressure = 0.4 MPa resistance propanesulfonic acid, acrylamide and the membrane become more hydrophilic, contact
membranes MgSO4: 2000 ppm, 1-vinylimidazole (P(AMPS-co-Am-co-VI) angle decreased, charge become neural, smoother
NaClO: 2000 ppm surface
DF30 P(AMPS-co-AM-co-VI): • Permeability increased in lower coating concen-
0.5, 1, 2, 5 g/L tration and decrease slightly, salt rejection mono-
tonically increased and
• Chlorine resistance of the membrane increased
Commercial Temperature = 28 °C To improve antifouling Monomers HEMA-co-PFDA • Contact angle decreased for coated membrane [110]
(SWRO) Pressure = 800 psi property • On coated membrane a discontinuous and porous
membrane NaCl concentration = Composition: 40% PFDA foulant layer formed while a continuous and
20 g/L on the copolymer dense foulant layer on uncoated membrane
TFC-HR, AD • Better resistance to foulant deposition
• Slight water permeability decline for coated
membrane without sacrifice of salt rejection
 R.H. Hailemariam et al. / Advances in Colloid and Interface Science 276 (2020) 102100 17

RO membrane Temperature = 25 °C To improve antifouling Sulfonated polyvinyl alcohol (SPVA) or PVA • Smooth structure formed [120]
was Pressure = 1.55 MPa property with glutaraldehyde as the crosslinker • Antifouling property improved
fabricated by Effective membrane • Contact angle decreased with coating of PVA
IP area = 42.2 cm2. PA-PVA-0.5 (51.4 ± 1.6°) and SPVA (35.2 ± 0.9°)
NaCl = 2000 ppm PA-SPVA-0.5 • Coated membrane showed more negatively
charged
• Water flux decrease slightly
• Rejection increase for all cases
• Fouling resistance for PA-SPVA-xx membranes
increased
SWC1), – Investigate amphiphilic Hydroxyethyl methacrylate (HEMA) and Amphiphilic copolymer [121]
TF-RO-SG copolymer coating for perfluorodecyl acrylate (PFA),
and TFC-HR biofouling control
• Delay formation of biofilm on membrane, it
HEMA-PFA
restrict the but does not prevent formation
• Delayed the increased pressure drop
• Influence biofilm composition (reduce polysac-
charide in 23% and protein in 132%) relatively
with the uncoated membrane
Prepared TFC Temperature = 25 °C To improved chlorine Polyethylene glycol diacrylate (PEGDA) • Contact angle decreased [114]
polyamide Pressure = 20 bar resistance • Smooth surface formed
membrane Effective membrane Concentration.; (10, 20, 30, 50, 70 and 90 • With increasing of PEGDA concentration water
by IP area = 36 cm2 wt% PEGDA in ultra-pure water) flux decreased and salt rejection and chlorine
NaCl = 2000 ppm resistance increased
Prepared TFC Temperature = 25 °C To improve the Organic-inorganic hybrid material by • Smooth and even flat surface formed [122]
polyamide Pressure = 1.55 MPa hydrophilicity and coating of polyvinyl alcohol (PVA) and • Contact angle increases with increased
membrane Effective membrane fouling resistance 3-mercaptopropyltriethoxysilane (MPTES) concentration, of MPTES
by IP area = 42.2 cm2 aqueous solution • Reduce negative charge density
NaCl = 2000 ppm • With increasing MPTES content the PA-MPTES-xx
membranes show reduction in water flux from
26.3 L m−2 h−1 to 17.9 L m−2 h−1 and increased
salt rejection from 98.14% to 98.85%
• PA-MPTES showed improved BSA and CTAB foul-
ing resistance
Commercial Temperature = 25 °C To improve boron sorption of hydrophobic long-chain • Lower boron passage (2–4 times) [123]
fully Pressure = 40 bar rejection aliphatic amine molecules as a generic • No change in surface morphology and chemistry
aromatic pH = 7–7.3 approach • Moderate flux drop with no change of salt
polyamide Membrane surface rejection
(PA) area = 2.8 m2
membrane NaCl = 15,000 ppm
SW30–2540 and Boron = 5 ppm
(Dow)

Chemically modifying the surface of PA-TFC RO membrane by
treating it with hydrofluoric (HF) and fluosilicic acids (FSA) helped to
increase the water flux [125]. Compared to the elemental fluorine, HF
and FSA are better for the modification of the membrane because they
require low reactor cost, are easy to handle, and are safe. Because of
the surface etching and partial fluorination, the flux in the modified
membrane exhibits a drastic increase without affecting the membrane's
rejection capacity.
Polar aprotic acids including hydrochloric, sulfuric, hydrofluoric, nitric,
and phosphoric acids, and other alcohols have been applied as hydroph-
ilizing agents for surface modification of TFC RO membranes [126]. Addi-
tion of ethanol, 2-propanol, hydrofluoric acid, and hydrochloric acid
increase water flux with no loss in salt rejection; however, the other acids
result in an increase in permeability with a slight reduction in rejection.
Grafting of hydrophilic polymer on the membrane surface was ex-
amined for the modification of RO membrane. The radicals are gener-
ated by a redox system containing potassium metabisulfite and
potassium persulfate. The formation of radicals attacked the backbone
of the polymer, and the monomers start latching on to membrane sur-
face by graft polymerization. Some of the monomers used in the poly-
merization process included methacrylate, AA, polyethylene glycol,
methacrylic acid, and sulfopropyl methacrylate. Attenuated total reflec-
tion Fourier transform infrared spectroscopy (ATR-FTIR) was used to
measure the extent of grafting on the surface of the membrane and all
the grafted-polymer-related changes in the absorption.
The RO membrane was modified by 1-ethyl-3-(3-dimethylamin-
opropyl)carbodiimide (EDC)-induced grafting with hydrophilic PEG de-
rivatives [127], which enhanced its hydrophilicity. After subjected to a
protein and cationic surfactant feed solution, the membrane exhibited
more resistance to fouling compared to the unmodified membrane.
However, the modification showed an acceptable decrease in
water flux due to the additional coating layer and no change in
rejection.
6-Aminocaproic acid (ACA) was used to modify the PA layer by in-
troducing IP between ACA and TMC. After the polymerization, a lyso-
zyme on the modified layer was immobilized by an amine coupling
reaction using 1-ethyl-3-(3-dimethylaminopropyl), EDC, and N-
hydroxysuccinimide. This immobilization resulted in a reduction in
water flux while maintaining the salt rejection ratio. Furthermore, the
prepared membrane exhibited sufficient antibacterial property against
Micrococcus lysodeikticus, a gram-positive bacteria, and Bacillus subtilis
and prevented a biofilm formation.
A facial two-step chemical surface modification via aldehydes was
proposed to fabricate a chlorine-resistant, high-performance PA TFC
membrane [128]. Firstly, formaldehyde was used to reduce the
chlorine-sensitive sites with N\\H bonds from the PA layer, then glutar-
aldehyde (GA) was introduced to crosslink the newly formed N-CH2OH
groups by stable ether bonds to tighten the polyamide inter chains. The
modified membrane showed ameliorative chlorine resistance both in
the alkaline and acidic aging conditions.
Sequential treatment of the membrane with GA and polyvinyl alco-
hol (PVA) was applied for membrane modification [129]. The PVA at-
tachment on the membrane's surface resulted in a reduction of a
surface negative charge, enhanced surface hydrophilicity, and a slightly
increased surface roughness. The modified membrane showed an im-
proved membrane chlorine resistance and enhanced antifouling prop-
erty of the membrane for foulants of sodium dodecyl sulfate (SDS),
bovine serum albumin (BSA), and dodecyltrimethyl ammonium bro-
mide. Furthermore, the modification enhanced water permeability
and rejection simultaneously.
18 R.H. Hailemariam et al. / Advances in Colloid and Interface Science 276 (2020) 102100

Table 4
Chemical surface modification of the active layer in the PA-TFC RO membranes in recent years; membrane type, experiment condition, purpose, and performance.

Membrane Experimental Objective Grafting agent and method of modification and Performance after modification Ref.
condition concentration

Commercial Pressure = 500 psi To improve Chemical Coupling • Increase surface hydrophilicity, which [131]
pristine PA TFC NaCl concentration = membrane poly(acrylic acid) (PAA- silane) enhance fouling resistance
membranes 3000 ppm surface • Contact angle decreased to 25 from 58 °C
wettability PAA: 0.2, 0.5, 1, 2.5, 10 wt% in • No reduction in membrane performance
SWC4+ methanol
Commercially Temperature = 25 °C To improve Redox initiated graft polymerization • Water flux increase by 22.55% from unmod- [132]
available Pressure = 1.5 MPa water flux and ified membrane without affecting salt rejec-
aromatic Effective membrane bio-fouling N,N′-dimethylaminoethyl methacrylater (DMAEMA) tion
polyamide RO area = 17.34 cm2 resistance followed by reacted with 3-bromopropionic acid • Surface charge neutralized
membrane NaCl concentration = (3-BPA) to get carboxybetaine methacrylate(CBMA) • By decreased to 16 °C (for pristine mem-
2000 ppm polymer brane 36 °C)
RE4021-TE • Improved resistance to protein adsorption
DMAEMA: (0.05, 0.1, 0.2, 0.3) mol/L and antimicrobial
• Improved antimicrobial property
Commercial Temp = 25.0 ± 0.1 °C To improve Chemical Coupling • Decreased contact angle [133]
available Pressure = 1.55 MPa antifouling • Smoother membrane surface with increas-
aromatic NaCl concentration = property Polyvinylamine (PVAm) (Grafting), PVA (Dip ing concentration
polyamide RO 2000 ppm coating) • Decreased negative charge density
membrane • With increased PVAm content water flux
PVAm; (0.05 w/v%, 0.10 w/v%, 0.20 w/v%, 0.25 w/v %) deceased and salt rejection increased
RE4021-TE, PVA: 1.0 w/v% • higher flux recovery for foulants
• PVAm grafted membrane showed a better
BW30FR, antifouling property than PVA coated mem-
LFC3 brane due to steric repulsion and neutral
surface charge
Commercial Temperature = 25 °C Improving Polyvinyl alcohol (PVA) • Contact angle and surface roughness [134]
available Pressure = 5 bar fouling decreased with increasing PVA content
aromatic PH = 7.0 resistance and PVA: 100, 300, 500, 1000 mg/L • Surface charge decreased
polyamide RO Effective membrane chlorine • Water flux slightly decreased and salt rejec-
membrane area = 19.0 cm2 stability tion increased
NaCl concentration = • Chlorine and alkaline resistance improved
Tianchuang RO 500 mg/L • Fouling resistance to SDS,BSA and DTAB
enhanced
Commercial Temperature = 25 °C To improve Chemical coupling • Contact angle decreased with increasing PVA [129]
pristine PA TFC Pressure = 5.0 bar membrane • Negative surface charge decrease and
membranes PH = 7.0 performance Glutaraldehyde(GA) followed by Polyvinylalcohol roughness increased with increased PVA
effective membrane (PVA) • Pure water flux increased with PVA content
Hangzhou area = 19.6 cm2 b150 mg/L
Tianchuang RO NaCl concentration = PVA concentration.: 50, 100, 150, 200 mg/L • Increased salt rejection, while water flux
500 mg/L slightly decreased
Improved membranes chlorine and antifouling
stability
Prepared TFC Temperature = 25 °C To enhance Chemical coupling • Contact angle decreased to 42.8 °C from 62.2 [128]
polyamide Pressure = 1.6 MPa chlorine °C for unmodified membrane
membrane by IP NaCl concentration = resistance Two-step modification by Aldehydes • Surface roughness remain same
2000 ppm Formaldehyde: to reduce chlorine sensitive site • Water permeability 37.5 L/m2 h close to
(37–40 wt%) original one 41.6 L/m2 h.
Glutaraldehyde phosphoric acid: 85 wt% • Salt rejection 98.6%, close to original 98.7%
• Stable acid resistance
• Better antifouling property to BSA foulant
and enhanced chlorine resistance in alkaline
and acidic condition
Aromatic PA _ To improve UV irradiation assisted radical grafting • Contact angle decreased to 16° (for pristine [135]
membrane antifouling 2-[(methacryloyloxy)ethyl] membrane 36°)
ESPA-1 property dimethyl-(3-sulfopropyl) ammonium hydroxide • More hydrophilic, less negative charge sur-
(SPE) face formed
• Improved resistance to initial bacterial
SPE: 0.3 M adhesion
UV irradiation for 15 min Short term resistance to biofouling and organic
fouling improved.
A spiral-wound Temperature = 25 °C To improved Redox initiator • Contact angle decreased to 13° (for virgin [136]
commercial RO Pressure = 15.5 fouling Sol-gel coating method with silane coupling agent membrane 13°)
membrane kgf/cm2 resistance • Improved fouling resistance
effective membrane 3-glycidoxypropyltrimethoxysilane • For GPPTMS b1.0 wt% content, flux decline
SUL-H area = 27.0 cm2 (GPPTMS) index and fouling index decreased
NaCl concentration = GPPTMS: 0.5, 1, 1.5, 2 wt% in ethanol For N1.5 wt% GPPTMS concentration, the
2 g/L membrane less fouled and flux significantly
decreased
Commercial Temperature = 25 °C To improved Hydrophilic acrylic acid (AA, M) monomer and • Contact angle decreased with increasing of [137]
polyamide Pressure = 20 bar to hydrophilicity ethylene glycol dimethacrylate as a crosslinker AA
seawater RO 15 bar and fouling (EGDMA, 0.01 M) • Increases the membrane thickness
membrane NaCl concentration = resistance • Reduces roughness thus fouling decrease
2000 mg/L AA; (0.25, 0.5, 0.75, 1 and 1.5 M) • Negative charge increased High water flux
RE4040-SHF and Salt rejection reduced
 R.H. Hailemariam et al. / Advances in Colloid and Interface Science 276 (2020) 102100 19

Table 4 (continued)

Membrane Experimental Objective Grafting agent and method of modification and Performance after modification Ref.
condition concentration

Commercial Temperature = 22 °C To improve Grafting of a bioactive, non-biocidal • Water permeability decreased moderately [130]
membranes Pressure = 13.8 bar antifouling 2-aminoimidazole (2-AI) by coupling for ESPA3 by 13% and SWC4+ by 25%.
PH = 8 property 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide Increase biofilm inhibition property
ESPA3 and SWC4+ Active membrane area (EDC)
of 0.00146 m2
NaCl concentration = 2-AI; 0.44–1.08 M
500 mg/L
Commercial Temperature = 25 °C To prevent Surface-initiated atom transfer radical • Hydrophilicity increased [138]
polyamide RO Back pressure = 0.75 biofouling polymerization • Static bacterial adhesion improved
membranes MPa • Biofilm formation and biofouling effectively
Effective membrane Poly[(2-methacryloyloxy)ethyl]dimethyl prevented
ES20 area = 8.0 cm2 [3-sulfopropyl]ammonium hydroxide (pMEDSAH)
NaCl concentration = grafted on the surface of BIBB-immobilized
0.05 wt% membranes.
Commercial fully Temperature = 25 °C To improved Chemical coupling process • The amine incorporation reduce boron pas- [139]
aromatic Pressure = 55 bar boron rejection sage by a factor of 2–4
polyamide (PA) pH = 7–7.3 The coupling agent are 0.1 g • Some flux reduction observed
membranes Effective membrane N-(3-Dimethylaminopropyl)- • Flux-rejection tradeoff improved compared
area = 11.3 cm2 N′-ethylcarbodiimide hydrochloride to commercial PA membrane
SWC5 max NaCl concentration =
SWC4B 32,000 ppm
Boron concentration =
5 ppm

Grafting a polyamide RO membrane with non-biocidal 2-
aminoimidazole (2-AI) by activating the carboxylate groups in the ac-
tive layer with EDC [130] resulted in the enhancement of membrane
performance. In comparison to the unmodified membrane, grafting 2-
AI on the membrane significantly hindered (Pseudomonas aeruginosa)
the biofilm's growth. In Table 4, different recent chemical surface mod-
ifications on the PA-TFC RO membrane, and the corresponding mem-
brane type, experimental condition, and performance are summarized.
5. Conclusion and prospects
RO is most commonly used in the desalination industry as it is more
energy efficient and requires lower capital and operational costs com-
pared to other desalination methods. PA-TFC membranes currently
dominate the RO membrane applications because of advantages such
as excellent salt rejection and high water flux, wide operational pH
and temperature ranges, and stability. However, the performance of
the PA-TFC membrane is inhibited by tradeoffs between water perme-
ability and salt rejection, fouling, and scaling. Previous research works
have revealed that surface properties of the PA-TFC membranes, such
as surface hydrophilicity, roughness, and charge, strongly affect the
membrane's performance and fouling resistance. Consequentially,
membranes with high hydrophilicity, smoother surface, and low nega-
tive charge demonstrated better fouling resistance. Furthermore, the
current most commonly utilized IP process of RO fabrication method
provide a little control over the nano-pores of the polymer and layer
thickness that significantly cause limitations on the permeability of
the membrane. Among the existing strategies to tackle such problems,
CAIP and surface modification have proven to be effective approaches
to controlling and improving the surface properties of PA-TFC mem-
brane. The CAIP method will offer new degrees of freedom in modifying
polymer membrane with high separation performance. Addition of co-
solvents in the organic phase may alter the diffusivity, solubility, or re-
activity between the monomers, which may lead to changes in mem-
brane morphology, thickness, and structural network. Co-solvent
interfacial polymerization (CAIP) is one of the effective approaches to
eliminate any tradeoffs between permeability and rejection. The
added co-solvents increase the MPD diffusion rate in the organic
phase and decrease the solubility difference and interfacial tension be-
tween the two liquid phases, which in turn helps to form a loose
network layer with higher water permeability and salt rejection. How-
ever, for successful results, it is essential to choose carefully the appro-
priate monomers, experimental conditions, and type and
concentration of co-solvents. Acetone, diethyl ether, and ethyl acetate
are the mostly used co-solvents for the CAIP method. For instance, addi-
tion of ethyl acetate in small concentrations results in the formation of a
multi-layered PA structure with a desirable layer and an enhanced per-
formance when compared with other co-solvents. The CAIP approach in
the dodecane organic phase exhibited better salt rejection than in the
hexane solvent.
Even though the study in the membrane synthesis using co-
solvent has shown a promising result so far, there are still some
gaps which needs to be addressed and considered in future works.
For instance using co-solvents in different organic phase has
shown an enhanced performance however, the its effect on the
membrane fouling and scaling has not been yet discussed; The effect
of considering various experimental conditions and additional pa-
rameters needs to be addressed and optimized in detail as most of
the previous studies used almost same conditions and same type of
solvents; the membrane long term stability needs to be studied thor-
oughly during performance test.
Surface modification of the support layer plays an important role in
preparing a defect-free PA layer as it co-defines the interface where the
interfacial polymerization occurs; therefore, fine-tuning of the support
layer is essential to improve membrane performance. Active layer mod-
ification by physical and chemical treatments has been used for the re-
duction of surface roughness, to construct super hydrophilic surface
layer, introduce antibacterial layer, and improve the electrostatic sur-
face charge. However, for long-term operation, when compared to
chemical treatment, coating layers for physical modification is more
susceptible to washing in the chemical cleaning process due to the
weaker bonds between the coating material and the membrane surface.
In addition to that, in some cases, an additional layer formed after mod-
ification gives additional resistance to the membrane, which hinders the
passage of water and reduces the water flux. For this reason, a novel
coating agent with high stability and better applicability should be ex-
plored to increase chlorine resistance without reducing performance.
Moreover, some of the modification method are highly costly, and fol-
lows complicated synthesis and operational procedure which limits it
from commercial application.
20 R.H. Hailemariam et al. / Advances in Colloid and Interface Science 276 (2020) 102100
In summary, surface modification through physical, chemical
treatment, and co-solvent-assisted interfacial polymerization will
play an important role and open up new avenues in the fabrication
of polyamide membranes with improved performance (high water
permeability and salt rejection), as well as enhanced fouling and
chlorine resistance. From this review, we deduced that surface
modification and CAIP play the most important roles in enhancing
the performance of an RO membrane, which in turn will reduce the
cost of water production.
Acknowledgements
This research was supported by a grant (code-NRF-
2017M1A2A2047369) from research program funded by National Re-
search Foundation of Korea (NRF), Republic of Korea. R. H. Hailemariam
and M. M. Damtie also acknowledge admin support from the University
of Science & Technology (UST), Republic of Korea.
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