Desalination 326 (2013) 77–95

Contents lists available at ScienceDirect

Desalination
journal homepage: www.elsevier.com/locate/desal

A review on membrane fabrication: Structure, properties and

performance relationship
Boor Singh Lalia a, Victor Kochkodan b, Raed Hashaikeh a,⁎, Nidal Hilal a,b
a
Masdar Institute of Science and Technology, P.O. Box 54224, Abu Dhabi, United Arab Emirates
b
Centre for Water Advanced Technologies and Environmental Research (CWATER), College of Engineering, Swansea University, Swansea SA2 8PP, UK

H I G H L I G H T S

• Membrane fabrication techniques

• Structure–property relationship of membranes
• Structure parameters affect the membrane performance.

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

Article history: In this review, polymeric membrane fabrication techniques for pressure driven membrane processes and
Received 18 April 2013 membrane distillation are discussed. The fabrication technique, properties of the fabricated membranes
Received in revised form 18 June 2013 and performance in water desalination are related. Important parameters which affect the membrane perfor-
Accepted 20 June 2013
mance such as crystallinity of the membrane based polymer, porous structure, hydrophobicity/hydrophilicity,
Available online 16 August 2013
membrane charge and surface roughness are analyzed. Despite the fact that extensive knowledge exist
Keywords:
on how to ‘tailor’ membrane pore structure including its surface properties and cross-section morphology
Polymer membranes by selection of appropriate fabrication methods, there is still a challenge to produce reliable membranes
Membrane fabrication with anti-fouling properties, chemical resistance, high mechanical strength with high flux and selectivity.
Porous structure To ensure progress in membrane performance, further improvements are needed of common membrane fab-
Membrane performance rication techniques such as phase inversion and interfacial polymerization. At the same time, the potential of
novel fabrication techniques such as electrospinning and track-etching needs to be assessed. A comprehensive
understanding between structure-surface properties and performance is a key for further development and
progress in membrane technology for water desalination.
© 2013 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
2. Membrane fabrication methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
2.1. Phase inversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
2.1.1. Immersion precipitation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
2.1.2. Evaporation-induced phase separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
2.2. Interfacial polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
2.3. Stretching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
2.4. Track-etching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
2.5. Electrospinning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
3. Structure–property–performance relationship . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
3.1. Crystallinity of the polymer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
3.2. Pore structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
3.3. Surface properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88

⁎ Corresponding author. Tel.: +971 28109152.

E-mail address: rhashaikeh@masdar.ac.ae (R. Hashaikeh).

0011-9164/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.desal.2013.06.016
78 B.S. Lalia et al. / Desalination 326 (2013) 77–95

3.3.1. Hydrophilic–hydrophobic properties of membrane surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88

3.3.2. Surface charge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
3.3.3. Surface roughness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
4. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
List of
List of abbreviations
abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92

1. Introduction
According to the world population clock, the population exceeds
7 billion and will reach 10 billion by 2050. Pure drinking water would
be a major problem for the developing countries in the world. The
improvement in the efficiency and cost of water treatment is a major
challenge to overcome the scarcity of portable water. Different membrane
methods have been used for water treatment, including microfiltration
(MF), ultrafiltration (UF), nanofiltration (NF), reverse osmosis (RO) and
membrane distillation (MD) [1]. UF and MF are well-developed tech-
niques used for water treatment, whereas RO is widely used for water
desalination and purification. MD is a new developing technique and it
has potential for desalinating highly saline water [2,3]. The membranes
play a key role in membrane-based water treatment processes and deter-
mine the technological and economical efficiency of the aforementioned
technologies; membrane improvement can greatly affect the perfor-
mance of current technology. The material selection and pore size of the
membranes depend on the application for which it would be used.
Fig. 1 represents the average pore size requirement for membranes for
different water treatment processes.
Different fabrication techniques and polymers used for the prepa-
ration of polymeric membranes are summarized in Table 1. Details of
the fabrication techniques process and the material structural charac-
teristics will be discussed in the subsequent sections.
In this article, the recent development of polymeric membrane ma-
terials and membrane preparation methods with focus on structure–
property relationships for pressure-driven membrane processes and
MD will be discussed. This review article will provide a reference to
the researchers and manufacturers working on fabrication of mem-
branes and materials for water treatment.
2. Membrane fabrication methods
The selection of a technique for polymer membrane fabrication
depends on a choice of polymer and desired structure of the membrane.
The most commonly used techniques for preparation of polymeric mem-
branes include phase inversion, interfacial polymerization, stretching,
track-etching and electrospinning.
2.1. Phase inversion
Phase inversion can be described as a demixing process whereby the
initially homogeneous polymer solution is transformed in a controlled
manner from a liquid to a solid state [4]. This transformation can be
accomplished in several ways [5], namely:
(a) Immersion precipitation. The polymer solution is immersed in
a non-solvent coagulation bath (typically water). Demixing
and precipitation occur due to the exchange of solvent (from
polymer solution) and non-solvent (from coagulation bath),
that is, the solvent and non-solvent must be miscible.
(b) Thermally induced phase separation. This method is based on the
phenomenon that the solvent quality usually decreases when the
temperature is decreased. After demixing is induced, the solvent
is removed by extraction, evaporation or freeze drying.
(c) Evaporation-induced phase separation. The polymer solution is
made in a solvent or in a mixture of a volatile non-solvent, and
the solvent is allowed to evaporate, leading to precipitation or
demixing/precipitation. This technique is also known as a solu-
tion casting method.
(d) Vapor-induced phase separation. The polymer solution is exposed
to an atmosphere containing a non-solvent (typically water);
absorption of non-solvent causes demixing/precipitation.
However, among these techniques, immersion precipitation and
thermally induced phase separation are the most commonly used
method in the fabrication of polymeric membranes with various mor-
phologies [6,7].
2.1.1. Immersion precipitation
Immersion precipitation is a process where a polymer solution is cast
on a suitable support, then immersed in a coagulation bath containing a
non-solvent, where an exchange of solvent and non-solvent takes place
and the membrane is formed [8]. Schematic presentation of processes
after polymer solution immersion in a non-solvent bath is shown in
Fig. 2. The solvent diffuses into the coagulation bath (at a flux = J2)
whereas the non-solvent will diffuse into the cast film (at a flux = J1).
After a certain time the exchange of solvent and non-solvent proceeds
until the solution becomes thermodynamically unstable and demixing
takes place. A solid polymeric film finally is obtained with an asymmet-
ric structure. Usually at J2 ≫ J1 “skin” UF membranes with pore size of
10–300 Å are obtained, while at J2 = J1 mainly MF membranes with
pore size of 0.2–0.5 μm are fabricated.
For membrane technologies, the development of the first high-flux
anisotropic acetate cellulose (CA) RO membranes via immersion precip-
itation by Loeb and Sourirajan [10] was one of the most critical break-
throughs in desalination. Today, extensive knowledge exists on how
to ‘tailor’ the membrane's pore structure including its cross-section

Nanofiltration Microfiltration

Ultrafiltration

Membrane
Reverse osmosis distillation

0.1nm 1nm 10nm 100nm µm

1µ 10µm

Fig. 1. Average pore size of the membranes used in different membrane processes.
 B.S. Lalia et al. / Desalination 326 (2013) 77–95 79

Table 1
Summary of commonly used polymers and fabrication techniques for the preparation of polymeric membranes for water treatment processes.

Water treatment process Polymers used for membrane fabrication Fabrication techniques Average pore size of the membrane

RO Cellulose acetate/triacetate Phase inversion 3–5 Å

Aromatic polyamide Solution casting
Polypiperzine
Polybenziimidazoline
NF Polyamides Interfacial polymerization 0.001–0.01 μm
Polysulfones Layer-by-layer deposition
Polyols Phase inversion
Polyphenols
UF Polyacrylonitrile (PAN) Phase inversion 0.001 – 0.1 μm
Polyethersulfone (PES) Solution wet-spinning
Polysulfone (PS)
Polyethersulfone (PES)
Poly(phthazine ether sulfone ketone) (PPESK)
Poly(vinyl butyral)
Polyvinylidene fluoride (PVDF)
MF PVDF Phase inversion 0.1–10 μm
Poly(tetrafluorethylene) (PTFE) Stretching
Polypropylene (PP) Track-etching
Polyethylene (PE)
PES
Polyetheretherketone (PEEK)
MD PTFE Phase inversion 0.1–1 μm
PVDF Stretching
Electrospinning

morphology by the selection of polymer, solvents and non-solvents,
additives, precipitation time, bath temperature and other parameters
during immersion precipitation [11–17]. For example, different casting
conditions and post-treatments were proposed to improve the water
flux and salt rejection of the CA membranes [18–24]. Main polymers
used in membrane formation and their advantages and disadvantages
are presented in Table 2.
Apart from the chemical nature of a casting polymer, the concen-
tration of the polymer is very important in membrane fabrication via
immersion precipitation. Increasing polymer concentration in the
casting solution produces membranes with low porosity and pore
size. In this case, the macrovoid formation is suppressed and the ten-
dency to form sponge-like structures is enhanced. The UF membranes
are obtained within a range of polymer concentration of 12–20 wt.%,
whereas RO membranes are typically prepared from casting solutions
with polymer concentrations ≥ 20 wt.% [1].
Selection of solvent/non-solvent system also strongly affects
morphology and properties of casted membranes. The low miscibility
of polymer in the solvent leads to fabrication of a nonporous membrane,
while more porous membranes are obtained when the miscibility is
high. Generally aprotic solvents, where there are no hydrogen atoms
able to contribute to hydrogen bonding, are preferred for membrane
casting. An aprotic polar solvent such as N-methyl-2-pyrrolidone,
dimethyl formamide, dimethyl acetamide or dimethyl sulfoxide is
preferable for rapid precipitation (instantaneous demixing) upon im-
mersion in the non-solvent water and this produces anisotropic mem-
branes with a high porosity [6].
To improve the membrane morphology and properties, various
inorganic (such as LiCl) and high molecular weight organic (such as
polyvinyl pyrrolidone (PVP) or poly(ethylene glycol (PEG))) addi-
tives to casting solution are often used [29,30]. An additive can func-
tion as a pore former, increase solution viscosity or accelerate the
phase inversion process. For example, the effect of LiCl addition in
the membrane formation was investigated in the studies [31–35].
Fontananova et al. [32] found that LiCl addition in the PVDF/
dimethylacetamide dope increases flux of the casted membranes at
low LiCl concentration of 2.5 wt.%, but it suppressed macrovoid for-
mation at a high concentration of 7.5% LiCl and resulted in a decrease
of the membrane permeation flux. The similar results were obtained
by Lee et al. [33] for poly(amic acid) (PAA) casting solutions in
N-methyl-2-pyrrolidone. They found that by increasing LiCl concen-
tration in the PAA/N-methyl-2-pyrrolidone system, the solution
Table 2
Main polymers used in membrane formation via immersion precipitation [25–28].

Polymer Advantages Disadvantages

CA • Hydrophilicity •Low thermal resistance

• Flexibility in fabrication (b30 °C)
• Low cost •Low chemical resistance,
pH range (2–8)
• Poor resistance to chlorine
PS and • High thermal resistance •Low operating pressure limits
PES (up to 75 °C) • Hydrophobicity
• Wide pH tolerances (1–13)
• Good chlorine resistance
• Flexibility in membrane
fabrication (wide range
of pore size)
• High mechanical characteristics
PVDF •High mechanical strength • Hydrophobicity
and chemical resistance
Fig. 2. Schematic representation of a film/bath interface: J1 is the non-solvent flux and J2 the
•High thermal stability (up to 75 °C)
solvent flux. X is the position of the interface between the film and the coagulation bath, x is
Polyamide •Wide pH tolerance • Poor chlorine resistance
the spatial position coordinate normal to the membrane surface, y = −x − X(t) is the
(PA) •High thermal stability
position coordinate that moves with the interface. m is the position coordinate in the
•High mechanical properties
polymer-fixed frame of reference, and M is a support [9].
80 B.S. Lalia et al. / Desalination 326 (2013) 77–95
viscosity can be raised to the point where macrovoid formation is
hindered and development of a finely porous structure is favored.
The above observations were believed to be associated with the
change of the thermodynamic and kinetic properties of the polymer
dope system before and after LiCl addition. It was shown that LiCl
addition increased the dope's thermodynamic instability in reaction
with water, which facilitated a rapid phase demixing and resulted
in macrovoid formation (thermodynamic effect) [34]. On the other
hand, LiCl possesses strong interactions with the polymer and sol-
vent, which was supported by the significant increase in viscosity of
LiCl added casting solutions [31,33]. The strong interactions among
the components of the casting solution tended to delay the dope pre-
cipitation (the kinetic effect), which partially offset the thermodynamic
impact of LiCl addition. As a result, the size of the macrovoids in the
fabricated membranes is reduced at high LiCl dosage in the casting
solutions [33–35].
Saljoughi et al. [36] reported that an increase of PVP concentration
in the cast film from 0 to 1.5 wt.% resulted in the facilitation of
macrovoid formation in the membrane sub-layer, which increased
pure water flux. However, in the same study, it was observed that an
increase in PVP concentration from 1.5 to 3, 6 and 9 wt.% resulted in a
decrease in water flux, where the macrovoid had been suppressed grad-
ually. Wang et al. [37] showed that the PVP-added PES membrane has a
higher water flux and lower water contact angle than the neat PES
membrane. The contact angle decreased by 16% when the PVP content
in the casting solution was 10 wt.%. Ochoa et al. [38] proved that the
addition of PVP to the casting solution increases the UF PES membrane
permeability without significant changes in selectivity.
Marchese et al. [39] reported that the reasons behind the increase
of membrane permeability when PVP is added are an increment in
the pore density, a decrease of the effective thickness of the dense
layer due to macrovoids in the support layer and an increment in the
hydrophilicity of the surfaces on the membrane and inside the pores.
The formation phenomena of macrovoids, which are large elongated
spaces below the upper surface of the membrane, have been widely
discussed by Smolders et al. [12], Wang et al. [40], and McKelvey and
Koros [41].
Arthanareeswaran et al. [42] concluded that the presence of
low molecular weight PEG additive in the cast solution film increased
porosity/permeability of the prepared membranes. Saljoughi et al.
[43] studied the effects of PEG concentration (0 wt.%, 5 wt.% and
10 wt.%) on morphology, pure water permeation flux of the prepared
membranes at different coagulation bath temperatures (0 and 25 °C).
Increasing PEG concentration in the cast film results in the facilitation
of macrovoid formation in the membrane sub-layer, which increases
flux and rejection of human serum albumin. Susanto and Ulbricht
[44] compared the effect of three different macromolecular additives
PVP, PEG and poly(ethylene oxide)-b-poly(propylene oxide)-b-poly
(ethylene oxide) (Pluronic) on the membrane structure and their
stability in the polymer membrane matrix of the PES membrane.
They found that the addition of Pluronic as a modifier agent showed
the best membrane performance and stability. The authors suggest
that the reason for this phenomenon would be that the hydrophobic
part of Pluronic enhances the PES–additive interaction. Ultrafiltration
experiments also demonstrated that more than 70% of the initial
water flux could be recovered after UF of bovine serum albumin
(BSA) solution just by external cleaning with water. It was proposed
that a highly hydrated and dense poly(ethylene oxide) polymer
layer formed on the membrane surface prevented protein molecule
from contacting membrane surface directly, and the protein mole-
cules deposited on the poly(ethylene oxide) layer can be removed
easily by water washing.
Recently the use of inorganic nanoparticles as additives to polymeric
membranes has begun to attract wide interest due to the improved
membrane properties, including increased strength and modulus,
which result from the strong interfacial interactions the nanoparticles
have with the surrounding polymer matrix [45]. A comprehensive
review on polymeric membranes incorporated with metal/metal oxide
nanoparticles has been published recently by Ng et al. [46].
Zodrow et al. [47] prepared polysulfone membrane contained
Ag nanoparticles (1–70 nm) via the phase-inversion process by dis-
persing nanoparticles in the casting solution. It was shown that
polysulfone membranes impregnated with 0.9 wt.% Ag nanoparticles
possess similar permeability and surface charges compared with
pure polysulfone membranes, however they were significantly more
hydrophilic with 10% reduction in contact angle. It was found that
the addition of Ag nanoparticles does not visibly alter the membrane
structure. Similar results were obtained by Yan et al. [48], which used
nano-sized Al2O3 particles in dimethylacetamide casting solutions for
preparation of PVDF membranes. It was found that increased Al2O3
concentrations from 0 to 2% in the casting solution had led to in-
creased water permeate fluxes due to an increase in the membrane
hydrophilicity. SEM images showed that the addition of nano-sized
Al2O3 particles did not affect the surface, cross-section, and inner
pore membrane structures. Both pure PVDF and PVDF − Al2O3 mem-
branes showed typical asymmetric morphology with finger-like
pores.
On the other hand, Yang et al. [49] showed that the addition of TiO2
nanoparticles has a large effect on the membrane structure of TiO2/PS
membranes casted from 18 wt.% PS solution in N,N-dimethylacetamide
with N-methyl-2-pyrrolidinone. The cross-section morphologies of
membranes are shown in Fig. 3, which illustrates that the macrovoids
grow and become run through at low TiO2 concentrations and then
are suppressed or disappear at higher additive dosages (≥3 wt.%), the
thickness of skin layer increases with the increase of TiO2 dosage.
Fig. 4(a–c) shows a log-normal pore size distributions for the mem-
branes with TiO2 content of 1–2 wt.% and the number of small pores
increases compared with the PSF membrane without nanoparticles.
While adding more TiO2 (≥3%) to the casting solution enhances the
formation of larger pores (50–70 nm) caused by the nanoparticle
aggregate phenomenon, which leads to a bimodal pore distribution
(Fig. 4d). The mean pore radius of the membrane with 1–2 wt.% TiO2
content decreased and then increased at higher TiO2 content due to
the presence of large pores. These results demonstrate that adding
appropriate TiO2 nanoparticles to PS matrix can improve its porosity
and increase the number of small pores. As a result, the flux through
such membranes can be increased significantly. It was also shown that
the addition of TiO2 nanoparticles causes the decrease of contact angle
from 85° for pure PS membrane to 41–52° for TiO2/PS membranes, indi-
cating that TiO2 addition enhances the hydrophilicity of membrane as a
few of hydrophilic TiO2 nanoparticles adsorb and stick on the mem-
brane surface.
It should be mentioned however, that one of the limiting factors
for incorporation of nanoparticles into polymeric membranes is high
aggregation of nanoparticles that results in a low dispensability in
the casting solution. Also, careful control and monitoring of the nano-
particles released from the modified membranes are necessary to
minimize potential (eco) toxicity effects.
2.1.2. Evaporation-induced phase separation
Evaporation-induced phase separation is a facile technique to pre-
pare membranes for various applications. At the first stage, a sufficiently
viscous polymer solution is prepared in a solvent (or in binary/ternary
mixture of solvents) and a non-solvent. Then a prepared polymer solu-
tion is casted on a flat porous substrate using a doctor blade technique
[50]. When the volatile solvent evaporates from the casted solution, a
thin polymer film is formed on the porous support. The morphology
of the solution casted films can be controlled by using solvents with
different boiling points. Nguyen et al. [51] developed PVDF, PVC, PS
and PVAc microporous membranes using different organic solvents
and studied the effect of different solvents on the surface morphology
and pore size/shape. Kim et al. [52] prepared microporous polystyrene
 B.S. Lalia et al. / Desalination 326 (2013) 77–95 81

Fig. 3. SEM images of the morphology of PS/TiO2 membranes with (a) 0 wt.% TiO2, (b) 1 wt.% TiO2, (d) 3 wt.% TiO2, and (e) 5 wt.% TiO2 [49].

Fig. 4. Pore size distributions of PS/TiO2 membranes with (a) 0 wt.% TiO2, (b) 1 wt.% TiO2, (c) 2 wt.% TiO2, and (d) 3 wt.% TiO2 [49].
82 B.S. Lalia et al. / Desalination 326 (2013) 77–95

Fig. 5. SEM images of the surface morphologies of the porous silicon rubber membranes prepared at different liquid paraffin concentrations (a) 10, (b) 15, (c) 20, (d) 25, (e) 30 and
(f) 40 wt.% [53].

films using PEG used as pore former. The pore size of the membranes
was in the 5–12 μm range and controlled by varying polystyrene/PEG
concentrations and different molecular weights of PEG. Zhao et al. [53]
prepared silicon rubber microporous membranes using this technique.
The pore size and the pore structure of the membranes were tuned by
varying casting temperature and the concentration of liquid paraffin.
Fig. 5 showed the formation of porous silicon membranes with different
pore shapes and sizes.
2.2. Interfacial polymerization
Interfacial polymerization (IP) is the most important method
for commercial fabrication of thin-film composite (TFC) RO and NF
membranes. The first interfacially polymerized TFC membranes
were developed by Cadotte et al. [54] and represented a break-
through in membrane performance for RO applications [55]. The orig-
inal IP protocol involved soaking a microporous polysulfone support
in an aqueous solution of a polymeric amine and then immersing
the amine impregnated membrane into a solution of a di-isocyanate
in hexane. The membrane was then cross-linked by heat-treatment
at 110 °C [54]. The resulting TFC polyurea membrane had better salt
rejection than that of an integrally-skinned asymmetric cellulose
acetate membrane and high water flux [55].
Due to the significant advantages of IP technique in optimizing
independently the properties of skin layer and microporous substrate
layer, a wide variety of TFC membranes have been successfully devel-
oped [56,57]. The various factors such as concentration of monomers,
solvent type, reaction time and post-treatment conditions affect the
structural morphology and composition of the barrier membrane
layer [57–60].
Most of NF and RO membranes produced by IP method have PA thin
layer on top of the membrane support. Among the used active monomers
to form functional PA layer in RO/NF membranes, m-phenylenediamine
(MPD) and trimesoyl chloride (TMC) are the most common (Fig. 6).
Other amine monomers for production of TFC PA membranes include:
p-phenylenediamine [61], piperazine [62], triethylenetetramine [63],
N-N′-diaminopiperazine [62], N-(2-aminoethyl)-piperazine [62], and
poly(ethyleneimine) [64].
Recently, novel monomers have been suggested for the prepara-
tion of TFC membranes via IP technique [62,64]. These monomers
contain more functional or polar groups, so the prepared membrane
exhibits smoother surface or better hydrophilicity, which is advanta-
geous to the improvement of antifouling property of the membranes.

Fig. 6. Preparation of thin film PA membrane from m-phenylenediamine (MPD) and trimesoyl chloride (TMC) via IP [56].
 B.S. Lalia et al. / Desalination 326 (2013) 77–95
For example, Li et al. [65] synthesized two novel tri- and tetra-
functional biphenyl acid chloride: 3,4′,5-biphenyl triacyl chloride
and 3,3′,5,5′-biphenyl tetraacyl chloride, which were then used to pre-
pare TFC RO membranes with MPD. Similarly, Liu et al. [66] presented
a novel RO composite membrane prepared from 5-isocyanato-
isophthaloyl chloride and MPD.
Besides the exploration of novel monomers for IP, the efforts have
been done on the improvement of IP process via adding of active
organic modifiers into TMC or MPD solutions. The modifiers can par-
ticipate in the reaction and are introduced into the functional barrier
layer, thus improving the surface property and fouling resistance
of resultant RO membranes. For example, Rana et al. [61] added
4,4′-methylene bis(phenyl isocyanate) and PEGs of average molecu-
lar weight 200 and 1000 Da into organic phase containing TMC to in-
corporate in situ hydrophilic surface modifying macromolecules. The
prepared membranes, which exhibited significantly more hydrophilic
surface, were then subjected to long term fouling studies using model
foulants including sodium humate, silica particles and chloroform
spiked in the feeding NaCl solution. The results showed that the flux
decline was reduced significantly after incorporating organic modi-
fiers into the TFC membranes. A similar approach was also used by
An et al. [67], who added polyvinyl alcohol (PVA) into piperazine
solution during IP to prepare low fouling NF membrane. It was also
shown that the addition of an acid-acceptor e.g. salt of triethylamine
with sulfonic acid in aqueous solution could speed-up IP reaction by
removing hydrogen halide by-products formed during amide bond
formation [68,69]. It was found that sodium lauryl sulfate or sodium
dodecyl sulfate could prevent pore collapse in PS substrate during
post-heat treatment of TFC membrane [70].
Many efforts have been done to improve chlorine stability of TFC
PA membranes against oxidative degradation [27,71]. It was noted
that the chemical modification of PA layer through the use of diamine
moieties could greatly enhance the chlorine resistance of the mem-
brane and the effectiveness of chlorine resistance is in the order of
aromatic, cycloaliphatic and aliphatic diamines, respectively [72].
Besides the TFC PA membranes, TFC polyester and polyesteramide
membranes were also developed via IP technique [73,74]. The incor-
poration of ester linkage increased the oxidation resistance of the
membrane and this significantly increased the membrane tolerance
on chlorine attack.
2.3. Stretching
Microporous membranes commonly used in MF, UF and MD are
fabricated by extrusion followed by stretching technique. Polymer
membrane fabrication using stretching was developed in 1970s and
its proprietary was owned the companies. Celgard® is known for pro-
ducing PE and PP based membranes for use in energy storage devices
Fig. 7. SEM image showing the patterned structure of the PTFE porous membranes produced by the stretching operation: (a) uniaxially stretched membrane, and (b) biaxially
stretched membrane prepared after the first stretching operation at the condition of (a) [82].
83
[75]. This is a solvent free technique, in which the polymer is heated
above the melting point and extruded into thin sheet forms followed
by stretching to make it porous [76–78]. This technique is suitable for
the highly crystalline polymers where the crystalline regions of the
polymer provide strength and amorphous regions formed the porous
structure. Usually, stretching is carried out in two steps, first cold
stretching followed by the hot stretching. Cold stretching is used to
nucleate the micropores in the precursor film followed by the hot
stretching to increase/control the final pore structure of membranes.
In this process, material's physical properties (like crystallinity,
melting point, tensile strength etc.) and the applied processing
parameters control the final porous structure and properties of the
membranes [76]. Carreau's research group reported PP membrane
fabrication by stretching and studied various factors affecting the
morphology and permeation [79–81]. They found that molecular
weight of PP is a key parameter to control the structure of the mem-
branes in addition to stretching (hot and cold) and annealing. In
another study, they developed blend membranes of long chain
branched PP and linear chain PP and studied the effect of blending
on the orientation of crystalline and amorphous in the precursor
film [80]. Addition of long branched PP improved the lamellae thick-
ness for the blend and increased the porosity of the blend membrane.
They also prepared porous membranes using PVDF of different melt
flow indexes and studied the effect of polymer melt rheology on
the row-nucleated lamellar morphology. The blending of PVDF with
different melt rheologies improved the water vapor permeability of
the PVDF membranes [81]. Kurumada et al. discussed the uniaxial
and biaxial stretching operations on the structure and morphology
of the PTFE membranes [82]. SEM images of the uniaxially and biaxi-
ally stretched membranes (Fig. 7) showed the effect of stretching on
the fibrils connecting the island like fraction of the film.
Tabatabaei et al. investigated the effect of blending (different mo-
lecular weights) PP on the crystallinity, pore density, pore uniformity
and tensile properties [83]. The increase in high molecular weight
species leads to more uniform pores, better connectivity and distribu-
tion of pores. The addition of high molecular weight PP does not sig-
nificantly influence the mechanical properties of the membranes. Kim
et al. studied the influence of annealing on crystallite size and crystal-
linity of precursor PP hollow fibers before the stretching process [84].
Un-annealed melt spun hollow fibers does not form pores upon hot
stretching. Pre-annealing of the precursor PP hollow fibers is found
to be essential for the formation of porous structure.
2.4. Track-etching
In this technique, a nonporous polymeric film is irradiated with
energetic heavy ions leading to the formation of linear damaged
tracks across the irradiated polymeric film. The schematic of single
84 B.S. Lalia et al. / Desalination 326 (2013) 77–95
ion-irradiation setup is shown in Fig. 8. This technique is famous for
its precise control on the pore size distribution of the membrane
and; pore size and pore density are independent parameters and
can be controlled in a wide range from a few nanometers to tens of
micrometers and 1–1010 cm−2 respectively. Due to these properties,
it makes a simple relationship between water transport properties
and membrane structure i.e. pore size/shape. Polycarbonate (PC) track
etched membranes were early available in 1970s [85]. The basic infor-
mation on the formation of particle tracks, track production mecha-
nism, track etching recipes and potential applications can be found in
the book by Fleischer et al. [86]. The membrane porosity is mainly
determined by the duration of irradiation, the pore size is determined
by the etching time and temperature. The resulting membranes have
a rather low porosity (up to 15%) or pore density (e.g. 6 × 108 cm−2
for 50 nm and 2 × 107 cm−2 for 1 μm) [86,87], in order to reduce the
probability of defects, i.e. double or triple pores. Under those conditions,
the pore size distribution can be very sharp [88]. There is some evidence
that the pore geometry for the smaller pore size track-etched mem-
branes may deviate from an ideal cylindrical shape, which can be
explained by the chemistry behind the manufacturing process [89].
Komaki et al. prepared porous polyethylene naphthalate (PET)
films irradiated by fission fragments obtained from thermal neutron
fission of uranium-235 and studied the effect of etching rate on the
hole diameter and hole density of the membranes [91]. In another
study, they first bombarded the polyimide films by several kinds
of heavy ions (127I, 107Ag, 79Br, 64Cu) and then treated with gamma
rays in the presence of oxygen. The growth of etched tracks increases
with gamma ray exposure in the presence of oxygen. This effect was
more prominent on the films bombarded with the lighter ions [92].
Starosta et al. irradiated PET films with heavy ion beams obtained
generated by cyclotron and chemically etched with NaOH solution.
The pore size was obtained in 0.1–0.5 μm [93]. In the above discus-
sion, PET and PC are most commonly used polymers for track etching
due to their stability towards acids, organic solvents and mechanical
properties. In addition, attempts were also made to use fluorinated
polymer viz. PVDF and its copolymers [94]. However, PVDF's resis-
tance towards strong oxidizers takes long hours for the formation of
pores.
2.5. Electrospinning
Electrospinning is a comparatively new technique to fabricate
porous membranes for various applications including filtration and
desalination [95–97]. A high potential is applied between the polymer
solution droplet and the grounded collector. When the electrostatic
potential becomes sufficiently high and overcomes the surface
tension of the droplet, a charged liquid jet is formed as shown in
Fig. 9. The unique features of these fibrous membranes are con-
trollable aspect ratios (aspect ratio = L/d; L—length of the fiber and
d—diameter of the fiber) and morphology of the nano/microfibers,
Fig. 8. Schematic showing single ion-irradiation setup used to fabricate track etched membrane [90].
which is achieved by varying the solution viscosity, environmental
conditions, applied electric potential and the flow rate of the solution
[98]. Porosity, pore size distribution, hydrophobicity and surface mor-
phology of the electrospun mats are controlled by the fiber diameter
and its morphology [96]. Due to the precise control on the fiber size,
shape and morphology electrospun fibrous membranes have been
used for filtration and MD processes [97,99–104]. Zong et al. investi-
gated the effect of polymer solution viscosity, applied potential
strength, solution feed rate and ionic salt addition (to improve the
conductivity of solution) on the fiber diameter and nanostructured
morphology [105]. Minimum potential difference of 20 kV was re-
quired to form a stable jet using 30 wt.% solution of poly(D,L-lactic
acid) in dimethyl formamide. The electrospun fibers with few beads
were obtained at 20 kV (keeping the feed rate and concentration of
polymer solution constant). Further increase in potential above
20 kV resulted in the formation of more beaded structure of the
fibers. Viscosity of the polymer solution also plays an important role
to form a beaded free smooth fibers, a minimum viscosity of solution
is needed to form smooth fibers which was 35 wt.% poly(D,L-lactic
acid) in dimethyl formamide in the present case. However, the mini-
mum viscosity requirements vary with the selection of polymers and
its molecular weights. Addition of salt (sodium chloride, sodium-/
potassium phosphate) was found to tune the diameter of the fibers,
fibers obtained from PDLA solution with 1 wt.% NaCl possessed the
smallest average fiber diameter. This was supposed to be due to the
increase in charge density on the jet results in a higher stretching
force on formation of fibers. Liu et al. discussed the formation of
poly(methyl methacrylate) (PMMA) polymer cup by playing with
the concentration of polymer solution in different solvents viz. ace-
tone, dimethyl formamide, methylene chloride, acrylonitrile, nitro-
methane and formic acid [106]. SEM images of different structures
prepared from PMMA solution in methylene chloride, acetone and
nitromethane were shown in Fig. 10.
Pai et al. studied the effect of non-solvent and humidity on the
morphology and fiber size of the polystyrene (PS) electrospun fibers
[107]. They found that fiber diameter of the PS fibers, electrospun
from 30 wt.% PS/DMF solution, increased from 0.9 μm to 3.93 μm
with an increase in relative humidity from 11 to 43%. The relative
humidity affects the solidification rate of electrospun fibers, the fibers
electrospun above 24 %RH had smooth surface. Below 24 %RH
the fibers have wrinkled surface. Due to the formation of wrinkles
at low RH, the diameter of the fibers becomes smaller.
Lin et al. studied the formation of micro- and nanoporous struc-
tures of the PS fiber by varying the solvent composition and solution
concentration of PS solution [108]. The fibers electrospun from
30 wt.% PS solution in THF showed ribbon like structure with densely
packed nanopores. With the addition of DMF in THF, nanopores dis-
appear and fiber surface becomes smooth. The decrease in concentra-
tion of PS in DMF/THF resulted in the formation of beaded structure of
nanofibers.
 B.S. Lalia et al. / Desalination 326 (2013) 77–95 85

Fig. 9. Schematic showing electrospinning of polymer solution.

Kaur et al. fabricated the PAN nano-fibrous membranes of differ- helped to improve the salt rejection of the membrane at the expense
ent fiber sizes by varying the concentration of PAN solution and of water flux. Further, the mean pore size, pore size distribution
they found that a decrease in the fiber size diameter decreases the and mechanical properties of the electrospun PAN membranes can
pore size of the microfiltration nano-fibrous membranes [109]. This be controlled by hot pressing. Hot pressing helps to fuse the fibers

Fig. 10. Electroprocessed structures from (a) 1.5 wt.% PMMA in methylene chloride, (b) 8 wt.% PMMA in acetone, (c) 4 wt.% PMMA in nitromethane, and (d) 16 wt.% PMMA in
nitromethane [106].
86 B.S. Lalia et al. / Desalination 326 (2013) 77–95
together and reduce the thickness of the electrospun membrane
and improve the mechanical as well as pore size distribution
[96,110]. Recently, Prince et al. studied the effect of incorporation of
nanoclay in the PVDF nanofiber membranes on the hydrophobicity
and performance in direct contact membrane distillation [95]. Addi-
tion of 8 wt.% nanoclay improves the membranes' contact angle
from ~ 128° to ~ 154° and salt rejection from 98.2% to 99.9% in a direct
contact membrane distillation process using 3.5 wt.% NaCl aqueous
solution. Kim et al. studied the effect of silica addition and thermal
treatment in PVDF nanofibrous membrane [111]. Improvement in
contact angle 128° to 134° with the addition of 40 wt.% tetramethyl
orthosilicate in PVDF nanofibrous membrane was observed. Further,
thermal treatment increased the surface roughness of the membrane
due to formation of silica particles by sol–gel reaction of tetramethyl
orthosilicate. The increase in surface roughness of the fiber further
increases the contact angle to ~ 145°.
3. Structure–property–performance relationship
Usually, the membrane performance (flux, rejection and fouling)
is strongly influenced by membrane polymer properties, porous struc-
ture and specific membrane surface features [112–114]. The most
important parameters, which affect the membrane performance, such
as crystallinity of the membrane based polymer, porous structure, hy-
drophobicity/hydrophilicity, membrane charge and surface roughness
are discussed in details below.
3.1. Crystallinity of the polymer
Crystallinity of polymers is a major property in determining
the mechanical stability and permeability of the polymer, particularly
for nonporous membranes. The glass transition temperature and
crystallinity are determined by the chain flexibility, chain interactions
and molecular weight of the polymer [115]. In general, most poly-
mers exist in the semi-crystalline (consist of amorphous and crystal-
line phases) form. In crystalline phase, the polymer chains are packed
in a regular pattern due to strong intermolecular interaction such
as hydrogen bonding in the case of PVA. The crystallites of polymer
are connected by the randomly oriented molecular chains known as
amorphous phase. The transport of liquid in NF (partially) and RO
membranes is accompanied by the sorption and diffusion and their
product yields the permeability (sorption × diffusion) of the perme-
able membrane. The crystallites of the polymers have highly packed
structure; liquid permeates cannot penetrate inside the packed struc-
ture and the transport of liquid takes place through the amorphous
layer. Peterlin et al. studied the effect of crystallinity, spatial distri-
bution of crystallites and fractional free volume on the sorption and
diffusion in polymers [116]. Diffusion coefficient and crystallinity of
the polymers can be described as [117]:

pore geometry and tortuosity. Kozeny–Carman modeled the relation-
n
Di ¼ Di;o Ψc =B ;
where Di,o diffusion coefficient at zero concentration, Ψc is the frac-
tion of crystalline material, B is constant and n is an exponential factor
(n b 1).
Gliozzi et al. studied the transport behavior of cross-linked colla-
gen membranes and found that filtration coefficient increases when
swelling of membrane increases in the amorphous state. The behavior
is opposite for the crystalline phase, the filtration coefficient decreased
when swelling increased in crystalline phase [118]. Gholap et al. grafted
N-tertiary butyl acrylamide on PVA molecular chains to improve the
hydrophobicity and reduces the swelling of the membrane. The heat
treatment of the membranes induces crystallinity which results in re-
duction of permeation flux through the membranes [119]. Lue et al.
discussed the correlation between the water diffusivity and free volume
of the PVA. The addition of silica in PVA increases the free volume hole
size and free volume hole density resulting in improvement in water
diffusivity related to decrease in crystallinity of the membrane [120].
Yu et al. reported that incorporation of higher concentration of SiO2
in the PVDF hollow fiber membranes resulted in a transition from
α-phase to β-phase crystal structure and restricted the movement of
PVDF. This led to deterioration of transport properties of the membrane.
However, PVDF–SiO2 membrane with 3 wt.% tetraethyl orthosilicate
(SiO2 precursor) improved the UF, antifouling, mechanical and thermal
properties [121]. Peng et al. studied the effect of degree of cross-linking
of PVA coating on the PS UF membranes performance. The increase in
PVA's degree of cross-linking improves the pure water permeability
and decreases the crystallinity of the PVA film [122,123]. Minelli et al.
investigated the effect of plasticization (glycerol as plasticizer) of
microfibrillated cellulose on the water sorption, diffusion coefficient
and structure of polymer films. The addition of plasticizers generally
increases the mobility of the polymer chains in plasticized material
which results in an improvement of water molecule diffusion [124].
Tseng et al. studied the effect of blending PVDF in the asymmetric cellu-
lose acetate propionate on the porosity, pure water flux and thermal
stability [125]. They found that up to 75 wt.% blending of PVDF, the
pure water flux improved. But, above 75 wt.% crystallization dominates
resulting in the reduction of flux and porosity of the membrane.
3.2. Pore structure
Water flux and solute rejection in NF, UF, MF and MD are primarily
controlled by the porosity, pore size distribution and pore tortuosity
of the membranes. The aforementioned properties of the membrane
are basically attributed by the pore geometry of the membranes.
Furthermore, the pore geometry of the membranes can be controlled
by choosing an appropriate fabrication technique. A relationship be-
tween fabrication technique and pore structure of the membrane
helps to design a membrane for particular application. Some charac-
teristic pore geometries of the membranes are illustrated in Fig. 11.
The simplest geometry of the membrane is characterized by paral-
lel cylindrical pores perpendicular to the membrane surface. Typical
example of parallel pore geometry is track etched membranes. The
pore length is equal to the thickness of the membranes. Hagen–
Poiseuille equation defines the permeate flux as:
εr 2 ΔP
J¼ ;
8ητ Δx
where J is solvent flux, ɛ is surface porosity, r is pore radius, ΔP
is pressure difference across the membrane of thickness Δx, η is vis-
cosity of the solution and τ is the pore tortuosity.
However, few membranes follow Hagen–Poiseuille equation,
because of different pore geometries. Membranes prepared by phase in-
version, stretching, solution casting and electrospinning have irregular
ship between flux and geometrical parameters of the membrane pores:
ε3 ΔP
J¼ ;
KηS ð1−εÞ2 Δx
2
where, ɛ is the volume fraction of pores, ΔP is pressure difference across
the membrane of thickness Δx, η is viscosity of the solution, K is
Kozeny–Carman constant (depends on the shape of the pores and tortu-
osity) and S is the internal surface area of the membrane pores.
In the phase inversion technique, the composition of the mem-
brane forming system and coagulation media control the porosity,
pore structure and pore size distribution of the membranes. Matsuura
and co-workers investigated the effect of hot water temperature
on the pore structure of CA membranes, effect of PVP additive in
PES membrane, dry jet-wet spinning conditions on the geometry of
hollow fiber membranes [30,129–131]. They found that hot water
 B.S. Lalia et al. / Desalination 326 (2013) 77–95
(a)
(c)
Fig. 11. SEM micrographs of (a) stretched high density PE microporous membranes, cold stretching of 55%, followed by hot stretching of 75% [126], (b) surface modified PES phase
inversion membranes [127], (c) track etched PC membrane irradiated with Kr ions [128] and (d) electrospun PVDF-co-hexafluoropropylene membrane [96].
treatment of cellulose, CA and cellulose triacetate membranes lead
to shrinkage of the surface pore size. Cellulose demonstrated high
resistance to shrinkage compared to CA/tri-acetate. This is due to
the highly ordered and close packed structure of cellulose i.e. due to
high crystallinity. Acetylation of cellulose reduces the crystallinity of
the cellulose and made it more sensitive to high temperature shrink-
age than native cellulose [129]. In other report, they investigated the
effect of addition of PVP in PES UF membranes. The strong interaction
between PES and PVP was observed when their weight ratio is in
unity. The interactions were supposed to be due to O_C\N b
unctional groups in the PVP and O_S_O functional group in the
PES polymer. These chemical interactions between PVP and PES
increased the largest pore size of the membranes resulting in an
increase in permeation flux through the membrane [30]. Recently,
the effect of polymer concentration and fabrication parameters on
the surface morphology, hydrophobicity, mean pore size and void
fractions of polyethereimide hollow fiber membranes were reported
by Matsuura and co-workers [132,133]. It was observed that increas-
ing PEI concentration in the spinning solution decreases the mean
pore size, effective surface porosity and formed the finger like
macrovoids (below the surface layer) of the membranes. The small
pores at the surface decrease the wettability of the membrane and
macrovoids decrease the mass transfer resistance. They modified
the hydrophobicity of the PEI hollow fiber membranes by introducing
surface modifying macromolecules. Modified-PEI membranes have
higher mean pore size, permeation rate, inner and outer surface con-
tact angles. Tiraferri et al. relates the structure of PS support layer
and performance of TFC membranes [134]. They varied the weight
ratio of n-methyl-2-pyrrolidone (NMP) and dimethyl formanide
(DMF) (kept the polymer concentration constant), solvents used for
87
(b)
(d)
solution preparation, and studied the formation of highly dense
support membrane using 100% DMF and highly porous structure
using 100% NMP. Also, the weight percent of the polymer was
changed and its effect on the porosity and pore shape of the PS mem-
brane was studied. They investigated how the transport properties of
the support layer and active layer are important to be optimized for
the high performance of the membranes. Penky et al. demonstrated
the visualization of development of macrovoid pores in dry caste cel-
lulose acetate/acetone/water solution using video-microscopy flow-
visualization. They explained the formation of macrovoids in three
stages namely fast initial growth, slow growth and collapse (active
collapse and passive collapse); and conclude that MV growth requires
a homogeneous supersaturated solution layer separating the demixed
fluid layer from a homogeneous stable solution layer. Supersaturated
solution layer provides the driving force to the growing macrovoid
[135]. Hernandez et al. studied the pore size distribution of track
etched membranes and found that permeability of the membranes
is determined by the bulk pore size distribution [136].
Wu et al. prepared PAN based symmetric membranes using
thermally induced phase separation technique and investigated the
effect of glycerol content, polymer concentration and cooling rate
on the pore shape, pore size, porosity, water flux and mechanical
properties of the membranes [137]. The increase in PAN concentra-
tion from 10 to 22 wt.% reduces the pore size of the membranes
from 5.3 to 0.8 μm and correlated this with the viscosity of the
solution. The membranes have cellular like pores for mixed diluent
(glycerol and dimethylsulfone) with 20–30 wt.% glycerol, whereas
needle like pores for 10–15 wt.% glycerol. The size of pores increases
when the temperature of the cooling water bath increases and the
same trend was observed when dried in air at different temperatures.
88 B.S. Lalia et al. / Desalination 326 (2013) 77–95
Zhao et al. prepared asymmetric PVDF membranes using solution
cast and electrospinning methods [138]. The effect of concentration
of PVDF and weight ratio of dimethyl formamide (DMF) and tetrahy-
drofuran (THF) solution on structure formation was studied. Increase
in polymer concentration from 5 to 8 wt.% in DMF/THF (5/5 w/w
ratio) leads to the formation of entangled polymer network with
small porosity and pore size. The effect of variation of solution con-
centration was studied by keeping the PVDF concentration constant
i.e. 5 wt.%. The increase in THF weight ratio in the solvent mixture
of THF/DMF results in the formation of small pores and porosity.
Razmjou et al. studied the effect of addition of TiO2 nanoparticles
(mechanically and chemically modified) on the membrane perfor-
mance and its structural and mechanical properties [139]. Addition
of mechanically modified TiO2 increases the number of microvoids in
the membrane whereas chemically and modified TiO2 nanoparticles
lead to elongation of finger like microvoids. These structural modifica-
tions with incorporation of TiO2 nanoparticles in the membrane im-
prove the pore size, porosity and hydrophilicity of the membrane
which results in an improvement of water flux through the modified
membrane.
Han et al. prepared the ultrafiltration membranes of carboxymethyl
cellulose acetate (CMCA)/cellulose acetate (CA) using phase inversion
method and studied the effect of addition of CMCA and polyethylene
glycol (PEG) on the structure of skin layer and sub-layer of the mem-
brane. Incorporation of CMCA and PEG caused the formation of more
pores and macrovoids beneath the skin layer. Addition of CMCA de-
creases the pure water contact angle on the surface of the membrane
and improved the pure water flux through the membrane.
3.3. Surface properties
3.3.1. Hydrophilic–hydrophobic properties of membrane surface
As known, the common-evaluation approach for hydrophilic-
hydrophobic properties of membrane is based on evaluation of a contact
angle formed between the liquid–gas tangent and membrane–liquid
boundary [61,140]. Most commercial membranes for pressure-driven
processes are made from hydrophobic polymers with high thermal,
chemical and mechanical stability. Usually these materials are charac-
terized by high contact angle values and are prone to adsorption of
the various solutes from feed streams [13].
The adsorption of hydrophobic compounds onto membranes may
be an important factor in solute rejection during membrane applica-
tions. Recently, it was shown [141,142] that membranes with larger
contact angles could reject and adsorb more mass per unit area of a
hydrophobic solute than a membrane characterized by a smaller con-
tact angle. Chang et al. [143] reported that the steroid estrone was
highly rejected with MF hollow fibers due to adsorption mechanism
despite of a wide pore size of the membrane. Estrone rejection
decreases with filtration time due to saturation of the adsorption
capacity of the membrane with solute. Similar studies examining
adsorption of hydrophobic compounds onto NF and RO membranes
found that the initial adsorption of hydrophobic compounds could
not be considered a long-term removal mechanism since solute sorp-
tion and rejection decreased with time [114,144–148].
Kiso et al. [148] reported that the rejection of hydrophobic mole-
cules by NF membranes increased linearly with affinity of the solute
for the membrane as expressed through the octanol–water distribu-
tion coefficient (Kow). Thus, hydrophobic interactions between the
solute and membrane are the dominant rejection mechanism for
hydrophobic compounds. On the other hand, Van der Bruggen et al.
[149] concluded that although the Kow value was the best parameter
to describe the hydrophobic adsorption of compounds to membranes,
molecular size of solute also played an important role.
Apart from the hydrophobic compounds, highly polar organic solutes
can also interact with membrane surfaces. Matsuura and Sourirajan
showed [150] that rejection of alcohols, phenols, and carboxylic acids
by porous CA membranes decreases when acidity and hydrogen bond-
ing ability of the solutes decreased. Taft and Hammett parameters,
which indicate an effect of the substituent group on polarity, were
found to correlate with the rejection of these compounds [150]. It was
assumed that highly polar compounds can sorb into CA membrane
material via hydrogen bonding, diffuse across the membrane and result
in negative rejection values due to subsequent flux decline. It was also
shown [149,151] that polar compounds with sizes similar to membrane
pore diameters caused the greatest amount of flux decline through pore
blocking or adsorption within the pores.
Apart from membrane rejection, hydrophilic–hydrophobic properties
of the polymer membrane have a crucial influence on its anti-fouling
property and permeate flux [152,153]. It has been well documented
that membranes with hydrophilic surfaces are less susceptible to fouling
with organic substances, microorganisms, and charged inorganic parti-
cles [154,155] due to a decrease in the interaction between the foulant
and the membrane surface.
Nabe et al. found [156] a direct correlation between an extent
of membrane fouling and hydrophilic properties of the membrane
surface. They showed that during filtration of bovine serum albumin
solution the relative flux decreases, which correlates with the mem-
brane fouling, with an increase of contact angle of the membrane
surface, i.e. with an increase in membrane hydrophobicity.
Due et al. [157] improved hydrophilicity and surface smoothness
of commercial UF PVDF membranes by surface coating with a PVA
aqueous solution followed by solid-vapor interfacial cross-linking
with glutaraldehyde. It was shown that during UF of surface water
with total organic carbon of 7 mg/l, the flux of the PVA/PVDF mem-
brane was 14% higher than that of the unmodified PVDF membrane
after 4 h of filtration and 95% higher after 18 h of filtration (Fig. 12).
As can be seen in Fig. 12, the flux of the modified membrane reached
a plateau with increasing operating time, while the flux for the
unmodified membrane kept decreasing thus indicating that foulants
continued to accumulate on the surface over time. Additionally, the
cake-fouling layer could also be more easily removed from the PVA
modified membrane by alkaline cleaning. The higher performance of
the modified membrane was related to the increasing in hydrophilic-
ity and smoothness of the membrane surface after coating with the
PVA layer.
The major reason for hydrophobic membrane fouling with organic
compounds is that there are almost no hydrogen bonding interactions
in the boundary layer between the membrane interface and water.
The repulsion of water molecules away from the hydrophobic mem-
brane surface is a spontaneous process with increasing entropy and
therefore foulant molecules have a tendency to adsorb onto mem-
brane surface and dominate the boundary layer. In contrast, the
membrane with the hydrophilic layer possesses a high surface ten-
sion and is able to form the hydrogen bonds with surrounding
water molecules to reconstruct a thin water boundary between the
membrane and bulk solutions. It is difficult therefore for hydrophobic
solutes to approach the water boundary and break the orderly struc-
ture because an increase of energy would be required to remove the
water boundary and expose the membrane surface [7]. Therefore an
increase in the hydrophilicity of the membrane surface is often a
key goal to reducing membrane fouling with colloids, microorgan-
isms and organic pollutants. For example, it was found that the im-
provement on hydrophilicity can favor enhancing the permeate flux
of RO membrane [152,158] due to increasing interaction between
membrane surface and water molecule via hydrogen bond and/or
electrostatic attraction.
It should be mentioned, however, that a contact angle on the mem-
brane closely related with its surface features, including functional
groups, zeta potential, and surface roughness [159,160]. It was demon-
strated that the increase of the density of surface hydrophilic-group,
such as -OH, and -NH2, is favorable for improving the membrane hydro-
philicity [161,162]. Tang et al. [163] reported that the contact angles
 B.S. Lalia et al. / Desalination 326 (2013) 77–95
Fig. 12. Variation of the normalized fluxes (Grand River water flux/clean water flux) between base PVDF and modified PVA/PVDF membranes at the beginning (a) and at the end
of UF (b). Duration of UF cycle is 2 h, followed by the membranes cleaning with NaOH solution [157].
of PVA coated RO membranes are smaller than those of uncoated
membranes, due to the presence of abundant -OH groups of PVA mac-
romolecules on the membrane surface. High zeta potentials and rough
surfaces of RO membranes are also favorable for the decrease of their
contact angles [152,164]. Generally, the rougher the RO membrane
surface, the smaller its contact angle [163]. It may be because the
rough surface increases the solid–liquid interfacial free energy, and the
larger free energy is favorable for the decrease of contact angle [164].
However, the effect of surface roughness on membrane contact angle
is smaller than that of surface functional groups.
Additionally, the contact angle of the membrane sample is affected
by sample pre-treatment, water temperature and water salinity. Li
et al. [165] showed that contact angles of polyamide RO membrane
gradually decrease from 69.1° ± 0.8° to 54.0° ± 0.5° with the NaCl
concentration increasing from 0 to 16.000 ppm. It was explained
that because a large amount of electronegative carboxyl and hydroxyl
groups is present on the membrane surface, these groups can adsorb
Na+ ions from the solution. These adsorbed cations can orient sur-
rounding water molecules by Coulombic attraction with the water-
negative dipoles [166]. Thereby, the interactions between the interfacial
water molecules and RO membrane surface are strengthened.
3.3.2. Surface charge
Electrostatic interactions between charged solutes and a porous
membrane have been frequently reported to be an important rejec-
tion mechanism [112,167–170]. These interactions depend on the
membrane charge which is usually quantified by zeta potential mea-
surements [112]. The membrane surface of RO, NF and UF mem-
branes often carries a negative charge to increase the rejection of
dissolved salts and minimize the adsorption of negatively charged or-
ganic foulants and microorganisms [171,172]. Negative charge on the
membrane surface is usually caused by sulfonic and/or carboxylic
acid groups in a skin membrane layer, which may be deprotonated
in feed solution. Yoon et al. [173] showed that rejection of perchlorate
ions by negatively charged NF and UF membranes was greater than
expected based on only steric/size exclusions for these membranes
due to an electrochemical interaction mechanism. Usually, increasing
the pH of feed solutions increases the negative surface charge of the
membranes due to an increase in dissociation of carboxylic/sulphonic
functional groups [171,174,175]. As a result, electrostatic repulsion
between a negatively charged solute and membrane increases.
Besides inorganic salts, the membrane charge also affects rejection
of charged organics. Hu et al. [176] and Schafer et al. [177] found that
low molecular weight but charged organic acids had higher rejections
by RO and UF membranes than larger neutral organics due to electro-
static repulsion. Ozaki and Li [178] studied the rejection of urea and
acetic acid, both having the same molecular weight, at different pH
ranges with an RO membrane (ES20, Nitto Denko). It was shown
89
that while the rejection of uncharged urea decreased slightly from
35 to 28%, the rejection of acetic acid increased from 32% in the neu-
tral form at pH 3 to 100% in the negatively charged form at pH 9. The
increase in the rejection of acetic acid at pH values above the pK; is
most likely caused by the increasing negative charge of the mem-
brane surface repelling the negatively charged ions of acetic acid.
On the other hand, the effect of membrane surface charge on
membrane pore structure, permeate flux and the rejection of un-
charged organics at various pH is somewhat contradictory. It has
been reported that the rejection of uncharged solutes decreased,
while permeate flux increased at high pH values (8–10) due to an in-
crease in pore size of a membrane caused by the electrostatic repul-
sion between the functional groups within the membrane [179].
Some studies have found small dependence of the rejection of
uncharged organics and permeate flux on pH [173,178]. It was also
found that increasing the pH of a feed solution leads to pore shrinkage
of UF membranes and subsequently decreased permeability and
increased rejection [177]. In addition, it has been reported that salts
present in the feed water could reduce the negative charge on a mem-
brane surface by “shielding” the charge [174]. It was found that the
Debye length was small at higher ionic strengths, the zeta potential
was more positive, electrostatic interaction was minimized within
the membrane, and the pore radii could shrink [180,181]. At low
ionic strength when the Debye length is longer and the zeta potential
is more negative, pore radii can increase in size to minimize electro-
static repulsion between the negative functional groups in membrane
body [180,182].
The electrostatic charge of membranes is a particularly important
consideration for the reduction of membrane fouling where foulants
are charged, which is often the case. When the surface and the
foulant have similar charge, electrostatic repulsion forces between
the foulants and the membrane prevent the foulant deposition on
the membrane thereby reducing the fouling [183,184]. For example
a negative surface charge of the membrane will have a beneficial
effect on separation proteins around neutral pH, because most of pro-
teins have also negative charge at such conditions [13]. It was shown
that most of the colloidal particles such as natural organic matter
(NOM) that deposit on the membrane surface are negatively charged
[185]. As a result, PVA coated highly negatively charged membranes
may exhibit stable flux due to the strong electrostatic repulsion
between negatively charged NOM and membrane [163]. Although,
as mentioned, to date RO/NF membranes are mainly negatively
charged, however, development of positively charged membranes
with high hydrophilicity and rejection for multivalent cations could
be also beneficial [186]. These membranes may be used for the recov-
ery of valuable cationic macromolecules in biotechnology. Similar to
the negatively charged surface, the positively charged membrane sur-
faces exhibited electrochemical repulsion against positively charged
90 B.S. Lalia et al. / Desalination 326 (2013) 77–95
proteins [187], and may be used for the removal of heavy metals and
dyes from water [188,189].
3.3.3. Surface roughness
There is a strong correlation between the membrane fouling
and the surface roughness for RO and NF membranes. It was shown
that RO hydrophilic CA membranes with smooth membrane surfaces
are less prone to colloidal fouling compared to the relatively more
hydrophobic and rougher PA membranes [190].
As seen in Fig. 13, fluxes for commercial RO (Hydranautics LFC-1,
Trisep X-20) and NF (Dow-FilmTec NF-70, Osmonics HL) membranes
during filtration of NaCl solution with addition of silica particles
decrease when surface roughness of the membrane samples increase.
A greater roughness increases the total surface area to which
foulants can be attached, and the ridge-valley structure favors accu-
mulation of foulants at the surface. As a result, membranes with
rougher surfaces are observed to be more favorable for foulants'
attachment resulting in faster fouling rates. With AFM technique
Vrijenhoek et al. [114] clearly showed that particles preferentially
accumulate in the “valleys” of rough membranes, resulting in “val-
ley clogging” which causes more severe flux decline than in smooth
membranes. Abu Seman et al. [191] also reported that irreversible
fouling of PES membranes increases with an increase of surface
roughness during filtration of humic acids.
Using an AFM adhesion force measurement technique, Bowen
et al. [192] characterized the interaction force between a colloidal
silica probe and a rough membrane surface. It was found that mem-
brane surface roughness significantly reduced electrostatic repulsion
between the colloid and the surface, and the valley regions experi-
enced a greater adhesion force.
On the other hand, Boussu et al. [193] suggested that while colloi-
dal fouling was affected by both membrane roughness and hydropho-
bicity, membrane hydrophobicity seems to play a more significant
role for promoting fouling. Similarly, Park et al. [194] also observed
lower fouling potential for smooth and hydrophilic semiaromatic
piperazine based PA membranes compared to the more hydrophobic
m-phenylene-diamine based fully aromatic membranes. These au-
thors attributed the greater anti-fouling tendency to the large repul-
sive acid–base interaction for the more hydrophilic poly(piperazine)
membranes.
While results on membrane fouling depending on surface rough-
ness seem fairly consistent (i.e., rougher membranes foul more
quickly and are harder to clean), contradictory findings are reported
on effect of surface roughness on membrane flux: higher surface rough-
ness can mean higher flux, lower flux or have no effect on flux. Hirose
et al. [113] suggested an approximately linear relationship between
membrane surface roughness and flux for cross-linked aromatic poly-
amide RO membrane, where permeability increased with increasing
surface roughness. The tests were conducted using 1500 ppm NaCl
solution (pH 6.5) at 15 bar pressure and 25 °C temperature. The linear
Fig. 13. Correlation between the surface roughness of commercial RO/NF membranes
and their flux decline for the filtration of 0.05 M NaCl solution, which contained
200 mg/L silica particles (0.10 μm). Plotted using the data of Table 1 from [114].
relationship was attributed to surface unevenness of the RO membrane
skin layer, which resulted in larger effective surface area.
Kwak and Ihm [195] did not find a linear relationship between
membrane surface roughness and flux in filtration tests with
thin film polyamide RO membranes. The performance tests were car-
ried out with 0.2% NaCl solution at 15 bar and 25 °C. However, the
roughest membrane did have the highest flux. On the other hand,
Stamatialis et al. [196] showed that the lower surface roughness of
CA and cellulose acetate butyrate membranes the lower the flux and
the higher the rejection during filtration of 3500 ppm NaCl solution
at operating pressure of 40 bar. However, no explanation of these
findings has been provided. Madaeni [197] also found that the rough-
er RO membrane the lower the permeation rate due to the adsorption
and trapping of ions on the rough surface membrane.
Moreover, Al-Jeshi and Neville [198] showed that linear correla-
tion between surface roughness and flux does not exist for the four
commercial Osmonics RO membranes.
In attempts to clarify the role that membrane morphology plays in
transport through composite structures Ramon et al. [199] simulated
the interactions between rough coating films and the underlying
porous support membrane. They showed that: i) permeability in-
creases with surface roughness if the roughness is created while pro-
ducing thin regions in the coating film, essentially reducing the base
film thickness; however, when roughness is formed on top of an
unvarying base film thickness, the permeability of the film decreases
with increased roughness; and ii) when surface roughness comes at
the expense of base film thickness, the thinner regions (“valleys”)
present locally higher flux (“hot spots”) than the thicker regions
(“peaks”), and hence, these hot spots may be points of initiation for
colloidal and organic deposition, as well as mineral scale formation.
Note that membrane surface roughness is not a fixed value and
can change upon varying the conditions the membrane is exposed
to. For example, it was found [198] that water adsorption on TriSep
X20 membrane causes up to 35% change in the membrane surface
roughness. Additionally up to 33% difference in surface roughness
was observed upon imaging different areas of the membrane. These
important factors are often ignored when establishing correlations
between roughness and membrane performance parameters.
It should be noted that while analyzing membrane fouling with
complex feed solutions different membrane surface properties should
be taken into account. Jin et al. [200], suggested when feed contains
both positively and negatively charged pollutants, a smooth hydro-
philic surface with no carboxylic moieties is presumably the best
membrane option. In their study, the membrane with a hydrophilic
PVA coating showed significantly better fouling resistance against
alginate compared to the membrane without PVA coating.
On the other hand, Tang et al. [201] found that fouling by humic acid
and surfactant was less significant for semi-aromatic PA membranes
(smooth and hydrophilic surfaces) under mild fouling condition.
However, membrane properties were completely masked by the
foulant layer and further fouling tended to be dominated by foulant–
deposited-foulant interaction under severe fouling conditions [202].
An overall comparison between the various methods of fabrica-
tion of polymer membrane, the membranes properties and perfor-
mance are presented in Table 3, which is our interpretation of the
available literature data. It should be noted, that here we only attempt
to give a general comparison, because it is quite complicated to inter-
pret and compare results not only for different fabrication methods
but even for the same fabrication technique. The reason for this is
that the formation of membranes with each of fabrication methods
depends on a large number of material- and process-specific parame-
ters. For example, the formation of membrane made by the immer-
sion precipitation depends on choice of the polymer, solvents and
additives, composition and temperature of the casting solution,
choice of the quench medium and its temperature, evaporation con-
ditions, casting thickness, type of membrane support material, drying
 B.S. Lalia et al. / Desalination 326 (2013) 77–95 91

Table 3
Membrane fabrication methods: fabrication parameters and membrane performance and properties.

Fabrication method Fabrication parameters Membrane performance Membrane properties

Simplicity Reproducibility Cost Flux Retention Antifouling properties Width of pore size distribution Surface roughness Surface charge

Phase inversion H H L H M M H H H
Interfacial polymerization H H L L H H L L H
Stretching M M M H L L M L L
Track-etching L H H L L M L L L
Electrospinning M M M H L M H M L

H — High; M — Medium, L — Low.

conditions, etc. Additionally many membrane properties may be solute rejection, the role of membrane structure and surface properties
influenced simultaneously with the same fabrication process. in membrane performance is still not thoroughly understood. A system-
It can be seen in Table 3 that membrane properties and per- atic work is still needed to clarify for example the role that membrane
formance can be tuned to larger extend through the discussed morphology plays in trans-membrane transport, the effect of surface
membrane fabrication methods. Phase inversion and interfacial poly- roughness on membrane flux during membrane treatment of complex
merization are probably the most versatile and cost effective mem- feed solutions with organic and inorganic species, the influence of
brane fabrication techniques for preparation of polymer membranes membrane surface charge on membrane pore structure at various pH,
in a wide range of pore sizes (from RO to MF membranes) with vari- or for studying foulant-membrane interactions under severe fouling
ous hydrophilic/hydrophobic and charged properties at high values conditions. Identification of these parameters and others which can
of average porosity. However in many cases the width of pore size effectively be used to predict relationships between membrane fabrica-
distribution for phase inversion membranes should be improved to tion, structure, surface properties and performance could be very mean-
provide better retention properties. The additional advantages of ingful for further development of membrane based technologies for
the interfacial polymerization include the possibility of tuning inde- water treatment.
pendently the properties of skin/support layers and a low surface
roughness of the prepared membranes, which are of great impor- List of abbreviations
tance for development of low fouling TFC polymer membranes for AFM atomic force microscopy
pressure-driven membrane processes. Stretching is a simple and BSA bovine serum albumin
low cost method for fabrication of highly porous hydrophobic mem- CA cellulose acetate
branes for MF and MD, while these membranes are still prone to DMF dimethyl formamide
organic and (bio) colloidal fouling. The track-etched polymer mem- HFP hexafluoropropylene
branes are usually in a MF range of pore sizes with low surface rough- IP interfacial polymerisation
ness and their unique futures are practically ideal cylindrical shaped Kow octanol–water distribution coefficient
pores and a very sharp pore size distribution. However because of MD membrane distillation
low surface porosity, the membrane fluxes are rather low. The other MF microfiltration
drawback of these membranes is high cost, obviously, due to techni- MPD m-phenylenediamine
cal complexity of their fabrication. With respect to electrospinning, NF nanofiltration
it is a very promising method for preparation of highly productive NMP n-methyl-2-pyrrolidone
hydrophobic membranes for MF and MD but is in need of further de- NOM natural organic matter
velopment in terms of pore size distribution, antifouling properties, PA polyamide
cost reduction and fabrication on a large scale. PAA poly(amic acid)
PAN polyacrylonitrile
4. Conclusions PC polycarbonate
PE polyethylene
In this review, relationships between the synthesis of polymer PEEK polyetheretherketone
membranes, their structure, surface properties and performance PEG poly(ethylene glycol)
were discussed. It was shown that to date remarkable progress has PES polyethersulfone
been made in the fabrications of membranes for water treatment. PET polyethylene terephthalate
However, there is still a challenge to produce reliable membranes Pluronic poly(ethylene oxide)-b-poly(propylene oxide)-b-poly
with anti-fouling properties, high mechanical strength, high tolerance (ethylene oxide)
on chlorine attack and minimal thickness of the membrane barrier PP polypropylene
layer to provide a high flux. To ensure progress in these fields, PPESK poly(phthazine ether sulfone ketone)
more efforts are needed for further improvement of common mem- PS polysulfone
brane fabrication methods as well as the development of new fabri- PTFE ` poly(tetrafluorethylene)
cation techniques. A comprehensive understanding between porous PVA polyvinyl alcohol
structure-surface properties and the performance of membranes in PVAc polyvinyl acetate
water treatment processes is crucial for further development of poly- PVDF polyvillidene fluoride
mer membranes and optimization of fabrication processes. Membrane PVP polyvinyl pyrrolidone
performance (flux, rejection and fouling) is strongly influenced by RO reverse osmosis
membrane chemical composition and specific features of porous struc- TFC thin film composite
ture and the membrane surface, including hydrophobic/hydrophilic TFE tetrafluorethylene
properties, membrane charge (zeta potential), surface roughness, pore THF tetrahydrofurane
size and pore size distribution. Despite numerous research studies TMC trimesoyl chloride
attempting to relate physico-chemical properties of membranes to UF ultrafiltration
92 B.S. Lalia et al. / Desalination 326 (2013) 77–95
References
[1] R.W. Baker, Membrane Technology and Applications, John Wiley & Sons, Ltd,
West Sussex, England, 2004.
[2] M. Khayet, T. Matsumura, Membrane Distillation: Principles and Applications,
Elsevier, Oxford, U.K., 2011
[3] A. Alkhudhiri, N. Darwish, N. Hilal, Membrane distillation: a comprehensive
review, Desalination 287 (2012) 2–18.
[4] E. Drioli, L. Giorno, Membrane Operations: Innovative Separations and Transfor-
mations, Wiley-VCH, 2009.
[5] M. Mulder, Basic Principles of Membrane Technology, Kluwer Academic
Publishers, 1996.
[6] I. Pinnau, B.D. Freeman, Formation and modification of polymeric membranes:
overview, Membr. Form. Modif. 744 (2000) 1–22.
[7] F. Liu, N.A. Hashim, Y.T. Liu, M.R.M. Abed, K. Li, Progress in the production and
modification of PVDF membranes, J. Membr. Sci. 375 (2011) 1–27.
[8] K. Boussu, B. Van der Bruggen, C. Vandecasteele, Evaluation of self-made
nanoporous polyethersulfone membranes, relative to commercial nanofiltration
membranes, Desalination 200 (2006) 416–418.
[9] P. Radovanovic, S.W. Thiel, S.T. Hwang, Formation of asymmetric polysulfone
membranes by immersion precipitation .1. Modeling mass-transport during
gelation, J. Membr. Sci. 65 (1992) 213–229.
[10] S.S.S. Loeb, Sea water demineralization by means of an osmotic membrane, 38
(1963) 117–132.
[11] H. Strathmann, K. Kock, P. Amar, R.W. Baker, Formation mechanism of asymmet-
ric membranes, Desalination 16 (1975) 179–203.
[12] C.A. Smolders, A.J. Reuvers, R.M. Boom, I.M. Wienk, Microstructures in phase-
inversion membranes .1. Formation of macrovoids, J. Membr. Sci. 73 (1992) 259–275.
[13] M. Ulbricht, Advanced functional polymer membranes, Polymer 47 (2006)
2217–2262.
[14] I.C. Kim, H.G. Yoon, K.H. Lee, Formation of integrally skinned asymmetric
polyetherimide nanofiltration membranes by phase inversion process, J. Appl.
Polym. Sci. 84 (2002) 1300–1307.
[15] H.J. Kim, R.K. Tyagi, A.E. Fouda, K. Jonasson, The kinetic study for asymmetric
membrane formation via phase-inversion process, J. Appl. Polym. Sci. 62 (1996)
621–629.
[16] Q.Z. Zheng, P. Wang, Y.N. Yang, D.J. Cui, The relationship between porosity and
kinetics parameter of membrane formation in PSF ultrafiltration membrane,
J. Membr. Sci. 286 (2006) 7–11.
[17] M. Amirilargani, E. Saljoughi, T. Mohammadi, M.R. Moghbeli, Effects of coagula-
tion bath temperature and polyvinylpyrrolidone content on flat sheet asymmetric
polyethersulfone membranes, Polym. Eng. Sci. 50 (2010) 885–893.
[18] G.J. Gittens, P.A. Hitchcock, D.C. Sammon, G.E. Wakley, The structure of cellulose
acetate membranes for reverse osmosis. Part I. Membranes prepared from a
dioxan based dope, Desalination 8 (1970) 369–391.
[19] P.M. Fahey, H.E. Grethlein, Improved cellulose acetate membranes for reverse
osmosis, Desalination 9 (1971) 297–313.
[20] D.V. Mehta, E.A. Meinecke, Influence of some processing variables on the proper-
ties of cellulose acetate membranes III. Temperature dependence of the desalina-
tion performance of membranes plasticized by various plasticizers, Desalination
10 (1972) 369–382.
[21] M. Matsuda, C. Kamizawa, H. Yoshitome, On the conditions of fabrication of
tubular cellulose acetate membranes, Desalination 27 (1978) 41–50.
[22] H.H. Schwarz, K. Richau, H.G. Hicke, Annealing effect in porous cellulose acetate
membranes, J. Membr. Sci. 34 (1987) 283–296.
[23] M.J. Han, D. Bhattacharyya, Characterization of reverse osmosis cellulose acetate
membranes by gas adsorption method: effect of casting variables and chlorine
damage, J. Membr. Sci. 62 (1991) 325–346.
[24] T. Mohammadi, E. Saljoughi, Effect of production conditions on morphology and per-
meability of asymmetric cellulose acetate membranes, Desalination 243 (2009) 1–7.
[25] S.X. Liu, J.T. Kim, Characterization of surface modification of polyethersulfone
membrane, J. Adhes. Sci. Technol. 25 (2011) 193–212.
[26] A.S. More, S.K. Pasale, P.P. Wadgaonkar, Synthesis and characterization of poly-
amides containing pendant pentadecyl chains, Eur. Polym. J. 46 (2010) 557–567.
[27] P.R. Buch, D.J. Mohan, A.V.R. Reddy, Preparation, characterization and chlorine
stability of aromatic–cycloaliphatic polyamide thin film composite membranes,
J. Membr. Sci. 309 (2008) 36–44.
[28] R.W. Baker, Membrane Technology and Applications, J. Wiley, Chichester, 2004.
[29] W.Y. Chuang, T.H. Young, W.Y. Chiu, C.Y. Lin, The effect of polymeric additives on
the structure and permeability of poly(vinyl alcohol) asymmetric membranes,
Polymer 41 (2000) 5633–5641.
[30] L.Y. Lafreniere, F.D.F. Talbot, T. Matsuura, S. Sourirajan, Effect of polyvinylpyrrolidone
additive on the performance of polyethersulfone ultrafiltration membranes, Ind.
Eng. Chem. Res. 26 (1987) 2385–2389.
[31] A. Bottino, G. Capannelli, S. Munari, A. Turturro, High-performance ultrafiltration
membranes cast from LiCl doped solutions, Desalination 68 (1988) 167–177.
[32] E. Fontananova, J.C. Jansen, A. Cristiano, E. Curcio, E. Drioli, Effect of additives in the
casting solution on the formation of PVDF membranes, Desalination 192 (2006)
190–197.
[33] H.J. Lee, J. Won, H. Lee, Y.S. Kang, Solution properties of poly(amic acid)-NMP
containing LiCl and their effects on membrane morphologies, J. Membr. Sci.
196 (2002) 267–277.
[34] L. Shi, R. Wang, Y.M. Cao, D.T. Liang, J.H. Tay, Effect of additives on the fabrication
of poly (vinylidene fluoride-co-hexafluropropylene) (PVDF-HFP) asymmetric
microporous hollow fiber membranes, J. Membr. Sci. 315 (2008) 195–204.
[35] D.L. Wang, K. Li, W.K. Teo, Porous PVDF asymmetric hollow fiber membranes
prepared with the use of small molecular additives, J. Membr. Sci. 178 (2000)
13–23.
[36] E. Saljoughi, M. Amirilargani, T. Mohammadi, Effect of poly(vinyl pyrrolidone)
concentration and coagulation bath temperature on the morphology, perme-
ability, and thermal stability of asymmetric cellulose acetate membranes,
J. Appl. Polym. Sci. 111 (2009) 2537–2544.
[37] H.T. Wang, T. Yu, C.Y. Zhao, Q.Y. Du, Improvement of hydrophilicity and blood
compatibility on polyethersulfone membrane by adding polyvinylpyrrolidone,
Fibers Polym. 10 (2009) 1–5.
[38] N.A. Ochoa, P. Pradanos, L. Palacio, C. Pagliero, J. Marchese, A. Hernandez, Pore
size distributions based on AFM imaging and retention of multidisperse polymer
solutes — characterisation of polyethersulfone UF membranes with dopes
containing different PVP, J. Membr. Sci. 187 (2001) 227–237.
[39] J. Marchese, M. Ponce, N.A. Ochoa, P. Pradanos, L. Palacio, A. Hernandez, Fouling
behaviour of polyethersulfone UF membranes made with different PVP, J. Membr.
Sci. 211 (2003) 1–11.
[40] D.M. Wang, F.C. Lin, T.T. Wu, J.Y. Lai, Formation mechanism of the macrovoids
induced by surfactant additives, J. Membr. Sci. 142 (1998) 191–204.
[41] S.A. McKelvey, W.J. Koros, Phase separation, vitrification, and the manifestation of
macrovoids in polymeric asymmetric membranes, J. Membr. Sci. 112 (1996) 29–39.
[42] G. Arthanareeswaran, P. Thanikaivelan, J.A. Raguime, M. Raajenthiren, D. Mohan,
Metal ion separation and protein removal from aqueous solutions using modified
cellulose acetate membranes: role of polymeric additives, Sep. Purif. Technol. 55
(2007) 8–15.
[43] E. Saljoughi, M. Amirilargani, T. Mohammadi, Effect of PEG additive and coagu-
lation bath temperature on the morphology, permeability and thermal/chemical
stability of asymmetric CA membranes, Desalination 262 (2010) 72–78.
[44] H. Susanto, M. Ulbricht, Characteristics, performance and stability of polyethersulfone
ultrafiltration membranes prepared by phase separation method using different
macromolecular additives, J. Membr. Sci. 327 (2009) 125–135.
[45] M.Z. Rong, M.Q. Zhang, Y.X. Zheng, H.M. Zeng, R. Walter, K. Friedrich, Structure–
property relationships of irradiation grafted nano-inorganic particle filled poly-
propylene composites, Polymer 42 (2001) 167–183.
[46] L.Y. Ng, A.W. Mohammad, C.P. Leo, N. Hilal, Polymeric membranes incorporated
with metal/metal oxide nanoparticles: a comprehensive review, Desalination
308 (2013) 15–33.
[47] K. Zodrow, L. Brunet, S. Mahendra, D. Li, A. Zhang, Q.L. Li, P.J.J. Alvarez, Polysulfone
ultrafiltration membranes impregnated with silver nanoparticles show improved
biofouling resistance and virus removal, Water Res. 43 (2009) 715–723.
[48] L. Yan, Y.S. Li, C.B. Xiang, S. Xianda, Effect of nano-sized Al2O3-particle addition on
PVDF ultratiltration membrane performance, J. Membr. Sci. 276 (2006) 162–167.
[49] Y.N. Yang, H.X. Zhang, P. Wang, Q.Z. Zheng, J. Li, The influence of nano-sized TiO2
fillers on the morphologies and properties of PSFUF membrane, J. Membr. Sci.
288 (2007) 231–238.
[50] R.F. Silva, M. De Francesco, A. Pozio, Solution-cast Nafion® ionomer membranes:
preparation and characterization, Electrochim. Acta 49 (2004) 3211–3219.
[51] Q.T. Nguyen, O.T. Alaoui, H. Yang, C. Mbareck, Dry-cast process for synthetic
microporous membranes: physico-chemical analyses through morphological
studies, J. Membr. Sci. 358 (2010) 13–25.
[52] J.-K. Kim, K. Taki, M. Ohshima, Preparation of a unique microporous structure via
two step phase separation in the course of drying a ternary polymer solution,
Langmuir 23 (2007) 12397–12405.
[53] J. Zhao, G. Luo, J. Wu, H. Xia, Preparation of microporous silicone rubber mem-
brane with tunable pore size via solvent evaporation-induced phase separation,
ACS Appl. Mater. Interfaces 5 (2013) 2040–2046.
[54] J.E. Cadotte, R.J. Petersen, R.E. Larson, E.E. Erickson, New thin-film composite
seawater reverse-osmosis membrane, Desalination 32 (1980) 25–31.
[55] J. Cadotte, R. Forester, M. Kim, R. Petersen, T. Stocker, Nanofiltration membranes
broaden the use of membrane separation technology, Desalination 70 (1988) 77–88.
[56] W.J. Lau, A.F. Ismail, N. Misdan, M.A. Kassim, A recent progress in thin film com-
posite membrane: a review, Desalination 287 (2012) 190–199.
[57] R.J. Petersen, Composite reverse-osmosis and nanofiltration membranes, J. Membr.
Sci. 83 (1993) 81–150.
[58] A.P. Rao, N.V. Desai, R. Rangarajan, Interfacially synthesized thin film composite
RO membranes for seawater desalination, J. Membr. Sci. 124 (1997) 263–272.
[59] I.J. Roh, A.R. Greenberg, V.P. Khare, Synthesis and characterization of interfacially
polymerized polyamide thin films, Desalination 191 (2006) 279–290.
[60] A.K. Ghosh, B.H. Jeong, X.F. Huang, E.M.V. Hoek, Impacts of reaction and curing
conditions on polyamide composite reverse osmosis membrane properties,
J. Membr. Sci. 311 (2008) 34–45.
[61] B.J. Abu Tarboush, D. Rana, T. Matsuura, H.A. Arafat, R.M. Narbaitz, Preparation of
thin-film-composite polyamide membranes for desalination using novel hydro-
philic surface modifying macromolecules, J. Membr. Sci. 325 (2008) 166–175.
[62] S. Verissimo, K.V. Peinemann, J. Bordado, Influence of the diamine structure on
the nanofiltration performance, surface morphology and surface charge of the
composite polyamide membranes, J. Membr. Sci. 279 (2006) 266–275.
[63] S.H. Huang, C.L. Li, C.C. Hu, H.A. Tsai, K.R. Lee, J.Y. Lai, Polyamide thin-film com-
posite membranes prepared by interfacial polymerization for pervaporation
separation, Desalination 200 (2006) 387–389.
[64] A.R. Korikov, R. Kosaraju, K.K. Sirkar, Interfacially polymerized hydrophilic
microporous thin film composite membranes on porous polypropylene hollow
fibers and flat films, J. Membr. Sci. 279 (2006) 588–600.
[65] L. Li, S.B. Zhang, X.S. Zhang, G.D. Zheng, Polyamide thin film composite mem-
branes prepared from 3,4′,5-biphenyl triacyl chloride, 3,3′,5,5′-biphenyl
tetraacyl chloride and m-phenylenediamine, J. Membr. Sci. 289 (2007) 258–267.
 B.S. Lalia et al. / Desalination 326 (2013) 77–95
[66] L.F. Liu, S.C. Yu, L.G. Wu, C.J. Gao, Study on a novel antifouling polyamide-urea
reverse osmosis composite membrane (ICIC-MPD) — III. Analysis of membrane
electrical properties, J. Membr. Sci. 310 (2008) 119–128.
[67] Q.F. An, F. Li, Y.L. Ji, H.L. Chen, Influence of polyvinyl alcohol on the surface mor-
phology, separation and anti-fouling performance of the composite polyamide
nanofiltration membranes, J. Membr. Sci. 367 (2011) 158–165.
[68] M.H. Liu, S.C. Yu, J. Tao, C.J. Gao, Preparation, structure characteristics and sepa-
ration properties of thin-film composite polyamide-urethane seawater reverse
osmosis membrane, J. Membr. Sci. 325 (2008) 947–956.
[69] M.A. Kuehne, R.Q. Song, N.N. Li, R.J. Petersen, Flux enhancement in TFC RO mem-
branes, Environ. Prog. 20 (2001) 23–26.
[70] M.R. Duan, Z. Wang, J. Xu, J.X. Wang, S.C. Wang, Influence of hexamethyl
phosphoramide on polyamide composite reverse osmosis membrane perfor-
mance, Sep. Purif. Technol. 75 (2010) 145–155.
[71] T. Kawaguchi, H. Tamura, Chlorine-resistant membrane for reverse-osmosis .1.
Correlation between chemical structures and chlorine resistance of polyamides,
J. Appl. Polym. Sci. 29 (1984) 3359–3367.
[72] N. Misdan, W.J. Lau, A.F. Ismail, Seawater Reverse Osmosis (SWRO) desalination
by thin-film composite membrane—current development, challenges and future
prospects, Desalination 287 (2012) 228–237.
[73] B.B. Tang, Z.B. Huo, P.Y. Wu, Study on a novel polyester composite nanofiltration
membrane by interfacial polymerization of triethanolamine (TEOA) and
trimesoyl chloride (TMC) I. Preparation, characterization and nanofiltration
properties test of membrane, J. Membr. Sci. 320 (2008) 198–205.
[74] U. Razdan, S.S. Kulkarni, Nanofiltration thin-film-composite polyesteramide
membranes based on bulky diols, Desalination 161 (2004) 25–32.
[75] T. Sarada, L.C. Sawyer, M.I. Ostler, Three dimensional structure of celgard®
microporous membranes, J. Membr. Sci. 15 (1983) 97–113.
[76] F. Sadeghi, Developing of Microporous Polypropylene by Stretching, Ecole
Polytechnique, Montreal, 2007.
[77] W. Zhu, X. Zhang, C. Zhao, W. Wu, J. Hou, M. Xu, A novel polypropylene micro-
porous film, Polym. Adv. Technol. 7 (1996) 743–748.
[78] K. Trommer, B. Morgenstern, Nonrigid microporous PVC sheets: preparation and
properties, J. Appl. Polym. Sci. 115 (2010) 2119–2126.
[79] F. Sadeghi, A. Ajji, P.J. Carreau, Analysis of microporous membranes obtained
from polypropylene films by stretching, J. Membr. Sci. 292 (2007) 62–71.
[80] F. Sadeghi, A. Ajji, P.J. Carreau, Microporous membranes obtained from polypro-
pylene blends with superior permeability properties, J. Polymer Sci., Part B:
Polymer Phys. 46 (2008) 148–157.
[81] F. Sadeghi, S.H. Tabatabaei, A. Ajji, P.J. Carreau, Effect of PVDF characteristics
on extruded film morphology and porous membranes feasibility by stretching,
J. Polymer Sci., Part B: Polymer Phys. 47 (2009) 1219–1229.
[82] K.-I. Kurumada, T. Kitamura, N. Fukumoto, M. Oshima, M. Tanigaki, S.-I.
Kanazawa, Structure generation in PTFE porous membranes induced by the uni-
axial and biaxial stretching operations, J. Membr. Sci. 149 (1998) 51–57.
[83] S.H. Tabatabaei, P.J. Carreau, A. Ajji, Microporous membranes obtained from
polypropylene blend films by stretching, J. Membr. Sci. 325 (2008) 772–782.
[84] J. Kim, S.S. Kim, M. Park, M. Jang, Effects of precursor properties on the prepara-
tion of polyethylene hollow fiber membranes by stretching, J. Membr. Sci. 318
(2008) 201–209.
[85] R.L. Fleischer, P.B. Price, R.M. Walker, Nuclear tracks in solids, Principles and
Applications, University of California Press, Berkeley, 1975.
[86] R. Robert, Louis Fleischer, Paul Buford Price, R.M. Walker, Nuclear Tracks in
Solids: Principles and Applications, University of California Press, Berkley and
Los Angles, California, 1975.
[87] Nuclepore® membranes, www.whatman.com/products/?pageIDZ7.57.291.22, (in).
[88] P. Apel, Track etching technique in membrane technology, Radiat. Meas. 34
(2001) 559–566.
[89] C.R. Martin, M. Nishizawa, K. Jirage, M. Kang, Investigations of the transport
properties of gold nanotubule membranes, J. Phys. Chem. B 105 (2001)
1925–1934.
[90] M.E. Toimil-Molares, Characterization and properties of micro- and nanowires
of controlled size, composition, and geometry fabricated by electrodeposition
and ion-track technology, Beilstein J. Nanotechnol. 3 (2012) 860–883.
[91] Y. Komaki, S. Tsujimura, Growth of fine holes in polyethylenenaphthalate film
irradiated by fission fragments, J. Appl. Phys. 47 (1976) 1355–1358.
[92] Y. Komaki, N. Ishikawa, T. Sakurai, Effects of gamma rays on etching of heavy
ion tracks in polyimide, Radiat. Meas. 24 (1995) 193–196.
[93] W. Starosta, D. Wawszczak, B. Sartowska, M. Buczkowski, Investigations of
heavy ion tracks in polyethylene naphthalate films, Radiat. Meas. 31 (1999)
149–152.
[94] V.V. Shirkova, S.P. Tretyakova, Physical and chemical basis for the manufacturing
of fluoropolymer track membranes, Radiat. Meas. 28 (1997) 791–798.
[95] J.A. Prince, G. Singh, D. Rana, T. Matsuura, V. Anbharasi, T.S. Shanmugasundaram,
Preparation and characterization of highly hydrophobic poly(vinylidene fluo-
ride) — clay nanocomposite nanofiber membranes (PVDF–clay NNMs) for desa-
lination using direct contact membrane distillation, J. Membr. Sci. 397–398
(2012) 80–86.
[96] B.S. Lalia, E. Guillen-Burrieza, H.A. Arafat, R. Hashaikeh, Fabrication and characteri-
zation of polyvinylidenefluoride-co-hexafluoropropylene (PVDF-HFP) electrospun
membranes for direct contact membrane distillation, J. Membr. Sci. 428 (2013)
104–115.
[97] R. Gopal, S. Kaur, Z. Ma, C. Chan, S. Ramakrishna, T. Matsuura, Electrospun
nanofibrous filtration membrane, J. Membr. Sci. 281 (2006) 581–586.
[98] N. Bhardwaj, S.C. Kundu, Electrospinning: a fascinating fiber fabrication tech-
nique, Biotechnol. Adv. 28 (2010) 325–347.
93
[99] C. Feng, K.C. Khulbe, T. Matsuura, R. Gopal, S. Kaur, S. Ramakrishna, M. Khayet, Pro-
duction of drinking water from saline water by air-gap membrane distillation using
polyvinylidene fluoride nanofiber membrane, J. Membr. Sci. 311 (2008) 1–6.
[100] M. Khayet, T. Matsuura, Chapter 7 — Formation of Nano-fibre MD Membranes,
Membrane Distillation, Elsevier, Amsterdam, 2011, pp. 163–187.
[101] S. Kaur, D. Rana, T. Matsuura, S. Sundarrajan, S. Ramakrishna, Preparation and
characterization of surface modified electrospun membranes for higher filtra-
tion flux, J. Membr. Sci. 390–391 (2012) 235–242.
[102] H. Maab, L. Francis, A. Al-saadi, C. Aubry, N. Ghaffour, G. Amy, S.P. Nunes, Syn-
thesis and fabrication of nanostructured hydrophobic polyazole membranes
for low-energy water recovery, J. Membr. Sci. 423–424 (2012) 11–19.
[103] R. Wang, Y. Liu, B. Li, B.S. Hsiao, B. Chu, Electrospun nanofibrous membranes for
high flux microfiltration, J. Membr. Sci. 392–393 (2012) 167–174.
[104] Z. Zhao, J. Zheng, M. Wang, H. Zhang, C.C. Han, High performance ultrafiltration
membrane based on modified chitosan coating and electrospun nanofibrous
PVDF scaffolds, J. Membr. Sci. 394–395 (2012) 209–217.
[105] X. Zong, K. Kim, D. Fang, S. Ran, B.S. Hsiao, B. Chu, Structure and process relation-
ship of electrospun bioabsorbable nanofiber membranes, Polymer 43 (2002)
4403–4412.
[106] J. Liu, S. Kumar, Microscopic polymer cups by electrospinning, Polymer 46
(2005) 3211–3214.
[107] C.-L. Pai, M.C. Boyce, G.C. Rutledge, Morphology of porous and wrinkled fibers of
polystyrene electrospun from dimethylformamide, Macromolecules 42 (2009)
2102–2114.
[108] J. Lin, B. Ding, J. Yu, Y. Hsieh, Direct fabrication of highly nanoporous polystyrene
fibers via electrospinning, ACS Appl. Mater. Interfaces 2 (2010) 521–528.
[109] S. Kaur, S. Sundarrajan, D. Rana, T. Matsuura, S. Ramakrishna, Influence of
electrospun fiber size on the separation efficiency of thin film nanofiltration
composite membrane, J. Membr. Sci. 392–393 (2012) 101–111.
[110] S. Kaur, R. Barhate, S. Sundarrajan, T. Matsuura, S. Ramakrishna, Hot pressing of
electrospun membrane composite and its influence on separation performance on
thin film composite nanofiltration membrane, Desalination 279 (2011) 201–209.
[111] Y.-J. Kim, C.H. Ahn, M.O. Choi, Effect of thermal treatment on the characteristics
of electrospun PVDF–silica composite nanofibrous membrane, Eur. Polym. J. 46
(2010) 1957–1965.
[112] C. Bellona, J.E. Drewes, P. Xu, G. Amy, Factors affecting the rejection of organic
solutes during NF/RO treatment — a literature review, Water Res. 38 (2004)
2795–2809.
[113] M. Hirose, H. Ito, Y. Kamiyama, Effect of skin layer surface structures on the flux
behaviour of RO membranes, J. Membr. Sci. 121 (1996) 209–215.
[114] E.M. Vrijenhoek, S. Hong, M. Elimelech, Influence of membrane surface proper-
ties on initial rate of colloidal fouling of reverse osmosis and nanofiltration
membranes, J. Membr. Sci. 188 (2001) 115–128.
[115] M. Mulder, Basic Principles of Membrane Technology, 2nd ed. Kluwer Academic
Publishers, Dordrecht, London, 1997.
[116] A. Peterlin, Dependence of diffusive transport on morphology of crystalline
polymers, J. Macromol. Sci. Part B 11 (1975) 57–87.
[117] J.G.A. Bitter, Effect of crystallinity and swelling on the permeability and selectivity
of polymer membranes, Desalination 51 (1984) 19–35.
[118] A. Gliozzi, A. Ciferri, The role of swelling, amorphous vs. crystalline content,
charge density, and applied stress on the transport properties of polymeric
films, J. Membr. Sci. 3 (1978) 131–148.
[119] S.G. Gholap, J.P. Jog, M.V. Badiger, Synthesis and characterization of
hydrophobically modified poly(vinyl alcohol) hydrogel membrane, Polymer 45
(2004) 5863–5873.
[120] S.J. Lue, D.-T. Lee, J.-Y. Chen, C.-H. Chiu, C.-C. Hu, Y.C. Jean, J.-Y. Lai, Diffusivity en-
hancement of water vapor in poly(vinyl alcohol)-fumed silica nano-composite
membranes: correlation with polymer crystallinity and free-volume properties,
J. Membr. Sci. 325 (2008) 831–839.
[121] L.-Y. Yu, Z.-L. Xu, H.-M. Shen, H. Yang, Preparation and characterization of PVDF–
SiO2 composite hollow fiber UF membrane by sol–gel method, J. Membr. Sci.
337 (2009) 257–265.
[122] F. Peng, Z. Jiang, E.M.V. Hoek, Tuning the molecular structure, separation perfor-
mance and interfacial properties of poly(vinyl alcohol)–polysulfone interfacial
composite membranes, J. Membr. Sci. 368 (2011) 26–33.
[123] F. Peng, X. Huang, A. Jawor, E.M.V. Hoek, Transport, structural, and interfacial
properties of poly(vinyl alcohol)–polysulfone composite nanofiltration mem-
branes, J. Membr. Sci. 353 (2010) 169–176.
[124] M. Minelli, M.G. Baschetti, F. Doghieri, M. Ankerfors, T. Lindström, I. Siró, D.
Plackett, Investigation of mass transport properties of microfibrillated cellulose
(MFC) films, J. Membr. Sci. 358 (2010) 67–75.
[125] H.-H. Tseng, G.-L. Zhuang, Y.-C. Su, The effect of blending ratio on the compati-
bility, morphology, thermal behavior and pure water permeation of asymmetric
CAP/PVDF membranes, Desalination 284 (2012) 269–278.
[126] S.H. Tabatabaei, P.J. Carreau, A. Ajji, Microporous membranes obtained from
PP/HDPE multilayer films by stretching, J. Membr. Sci. 345 (2009) 148–159.
[127] D.E. Suk, T. Matsuura, H.B. Park, Y.M. Lee, Development of novel surface modi-
fied phase inversion membranes having hydrophobic surface-modifying macro-
molecule (nSMM) for vacuum membrane distillation, Desalination 261 (2010)
300–312.
[128] P.Y. Apel, I.V. Blonskaya, S.N. Dmitriev, O.L. Orelovitch, B. Sartowska, Structure of
polycarbonate track-etch membranes: origin of the “paradoxical” pore shape,
J. Membr. Sci. 282 (2006) 393–400.
[129] T.D. Nguyen, K. Chan, T. Matsuura, S. Sourirajan, Effect of shrinkage on pore size
and pore size distribution of different cellulosic reverse osmosis membranes,
Ind. Eng. Chem. Prod. Res. Dev. 23 (1984) 501–508.
94 B.S. Lalia et al. / Desalination 326 (2013) 77–95
[130] S. Mok, D.J. Worsfold, A.E. Fouda, T. Matsuura, S. Wang, K. Chan, Study on the
effect of spinning conditions and surface treatment on the geometry and perfor-
mance of polymeric hollow-fibre membranes, J. Membr. Sci. 100 (1995) 183–192.
[131] K.C. Khulbe, C.Y. Feng, F. Hamad, T. Matsuura, M. Khayet, Structural and perfor-
mance study of micro porous polyetherimide hollow fiber membranes prepared
at different air-gap, J. Membr. Sci. 245 (2004) 191–198.
[132] G. Bakeri, A.F. Ismail, M. Shariaty-Niassar, T. Matsuura, Effect of polymer concen-
tration on the structure and performance of polyetherimide hollow fiber mem-
branes, J. Membr. Sci. 363 (2010) 103–111.
[133] G. Bakeri, A.F. Ismail, D. Rana, T. Matsuura, M. Shariaty, Investigation on the
effects of fabrication parameters on the structure and properties of surface-
modified membranes using response surface methodology, J. Appl. Polym. Sci.
123 (2012) 2812–2827.
[134] A. Tiraferri, N.Y. Yip, W.A. Phillip, J.D. Schiffman, M. Elimelech, Relating perfor-
mance of thin-film composite forward osmosis membranes to support layer
formation and structure, J. Membr. Sci. 367 (2011) 340–352.
[135] M.R. Pekny, J. Zartman, W.B. Krantz, A.R. Greenberg, P. Todd, Flow-visualization
during macrovoid pore formation in dry-cast cellulose acetate membranes,
J. Membr. Sci. 211 (2003) 71–90.
[136] A. Hernández, J.I. Calvo, P. Prádanos, F. Tejerina, Pore size distributions of
track-etched membranes; comparison of surface and bulk porosities, Colloids
Surf., A Physicochem. Eng. Asp. 138 (1998) 391–401.
[137] Q.-Y. Wu, L.-S. Wan, Z.-K. Xu, Structure and performance of polyacrylonitrile
membranes prepared via thermally induced phase separation, J. Membr. Sci.
409–410 (2012) 355–364.
[138] Z. Zhao, J. Zheng, B. Peng, Z. Li, H. Zhang, C.C. Han, A novel composite
microfiltration membrane: structure and performance, J. Membr. Sci. 439
(2013) 12–19.
[139] A. Razmjou, A. Resosudarmo, R.L. Holmes, H. Li, J. Mansouri, V. Chen, The effect
of modified TiO2 nanoparticles on the polyethersulfone ultrafiltration hollow
fiber membranes, Desalination 287 (2012) 271–280.
[140] L. Zou, I. Vidalis, D. Steele, A. Michelmore, S.P. Low, J.Q.J.C. Verberk, Surface
hydrophilic modification of RO membranes by plasma polymerization for low
organic fouling, J. Membr. Sci. 369 (2011) 420–428.
[141] K. Kimura, G. Amy, J. Drewes, Y. Watanabe, Adsorption of hydrophobic com-
pounds onto NF/RO membranes: an artifact leading to overestimation of rejec-
tion, J. Membr. Sci. 221 (2003) 89–101.
[142] T. Wintgens, M. Gallenkemper, T. Melin, Occurrence and removal of endocrine
disrupters in landfill leachate treatment plants, Water Sci. Technol. 48 (2003)
127–134.
[143] S. Chang, T.D. Waite, A.I. Schafer, A.G. Fane, Adsorption of trace steroid estrogens
to hydrophobic hollow fibre membranes, Desalination 146 (2002) 381–386.
[144] M. Taniguchi, J.E. Kilduff, G. Belfort, Modes of natural organic matter fouling
during ultrafiltration, Environ. Sci. Technol. 37 (2003) 1676–1683.
[145] W. Kuhnl, A. Piry, V. Kaufmann, T. Grein, S. Ripperger, U. Kulozik, Impact of col-
loidal interactions on the flux in cross-flow microfiltration of milk at different
pH values: a surface energy approach, J. Membr. Sci. 352 (2010) 107–115.
[146] T.H. Chong, A.G. Fane, Implications of critical flux and cake enhanced osmotic
pressure (CEOP) on colloidal fouling in reverse osmosis: modeling approach,
Desalin. Water Treat. 8 (2009) 68–90.
[147] L.F. Song, Flux decline in crossflow microfiltration and ultrafiltration: mecha-
nisms and modeling of membrane fouling, J. Membr. Sci. 139 (1998) 183–200.
[148] Y. Kiso, T. Kon, T. Kitao, K. Nishimura, Rejection properties of alkyl phthalates
with nanofiltration membranes, J. Membr. Sci. 182 (2001) 205–214.
[149] B. Van der Bruggen, L. Braeken, C. Vandecasteele, Evaluation of parameters de-
scribing flux decline in nanofiltration of aqueous solutions containing organic
compounds, Desalination 147 (2002) 281–288.
[150] T. Matsuura, S. Souriraj, Physicochemical criteria for reverse osmosis separation
of alcohols, phenols, and monocarboxylic acids in aqueous solutions using
porous cellulose acetate membranes, J. Appl. Polym. Sci. 15 (1971) 2905.
[151] B. Van der Bruggen, C. Vandecasteele, Flux decline during nanofiltration of
organic components in aqueous solution, Environ. Sci. Technol. 35 (2001)
3535–3540.
[152] Q. Li, X.H. Pan, C.Y. Hou, Y. Jin, H.J. Dai, H.Z. Wang, X.L. Zhao, X.Q. Liu, Exploring
the dependence of bulk properties on surface chemistries and microstructures
of commercially composite RO membranes by novel characterization approaches,
Desalination 292 (2012) 9–18.
[153] C.Y.Y. Tang, Y.N. Kwon, J.O. Leckie, Effect of membrane chemistry and coating
layer on physiochemical properties of thin film composite polyamide RO and
NF membranes I. FTIR and XPS characterization of polyamide and coating layer
chemistry, Desalination 242 (2009) 149–167.
[154] L.F. Liu, S.C. Yu, L.G. Wu, C.H. Gao, Study on a novel polyamide-urea reverse
osmosis composite membrane (ICIC-MPD) II. Analysis of membrane antifouling
performance, J. Membr. Sci. 283 (2006) 133–146.
[155] N. Hilal, O.O. Ogunbiyi, N.J. Miles, R. Nigmatullin, Methods employed for control
of fouling in MF and UF membranes: a comprehensive review, Sep. Sci. Technol.
40 (2005) 1957–2005.
[156] A. Nabe, E. Staude, G. Belfort, Surface modification of polysulfone ultrafiltration
membranes and fouling by BSA solutions, J. Membr. Sci. 133 (1997) 57–72.
[157] J.R. Du, S. Peldszus, P.M. Huck, X.S. Feng, Modification of poly(vinylidene fluoride)
ultrafiltration membranes with poly(vinyl alcohol) for fouling control in drinking
water treatment, Water Res. 43 (2009) 4559–4568.
[158] S.C. Yu, X.S. Liu, J.Q. Liu, D.H. Wu, M.H. Liu, C.J. Gao, Surface modification of thin-film
composite polyamide reverse osmosis membranes with thermo-responsive poly-
mer (TRP) for improved fouling resistance and cleaning efficiency, Sep. Purif.
Technol. 76 (2011) 283–291.
[159] T. Humplik, J. Lee, S.C. O'Hern, B.A. Fellman, M.A. Baig, S.F. Hassan, M.A. Atieh, F.
Rahman, T. Laoui, R. Karnik, E.N. Wang, Nanostructured materials for water
desalination, Nanotechnology 22 (2011).
[160] J. Gilron, S. Belfer, P. Vaisanen, M. Nystrom, Effects of surface modification on an-
tifouling and performance properties of reverse osmosis membranes, Desalina-
tion 140 (2001) 167–179.
[161] H. Zou, Y. Jin, J. Yang, H.J. Dai, X.L. Yu, J. Xu, Synthesis and characterization of thin
film composite reverse osmosis membranes via novel interfacial polymerization
approach, Sep. Purif. Technol. 72 (2010) 256–262.
[162] V. Freger, J. Gilron, S. Belfer, TFC polyamide membranes modified by grafting
of hydrophilic polymers: an FT-IR/AFM/TEM study, J. Membr. Sci. 209 (2002)
283–292.
[163] C.Y.Y. Tang, Y.N. Kwon, J.O. Leckie, Effect of membrane chemistry and coating
layer on physiochemical properties of thin film composite polyamide RO and
NF membranes II. Membrane physiochemical properties and their dependence
on polyamide and coating layers, Desalination 242 (2009) 168–182.
[164] M.L. Lind, D.E. Suk, T.V. Nguyen, E.M.V. Hoek, Tailoring the structure of thin film
nanocomposite membranes to achieve seawater RD membrane performance,
Environ. Sci. Technol. 44 (2010) 8230–8235.
[165] Q. Li, X. Pan, Z. Qu, X. Zhao, Y. Jin, H. Dai, B. Yang, X. Wang, Understanding the
dependence of contact angles of commercially RO membranes on external con-
ditions and surface features, Desalination 309 (2013) 38–45.
[166] Q. Du, E. Freysz, Y.R. Shen, Vibrational-spectra of water-molecules at quartz
water interfaces, Phys. Rev. Lett. 72 (1994) 238–241.
[167] X.L. Wang, T. Tsuru, S. Nakao, S. Kimura, The electrostatic and steric-hindrance
model for the transport of charged solutes through nanofiltration membranes,
J. Membr. Sci. 135 (1997) 19–32.
[168] X.L. Wang, W.N. Wang, D.X. Wang, Experimental investigation on separation
performance of nanofiltration membranes for inorganic electrolyte solutions,
Desalination 145 (2002) 115–122.
[169] W.R. Bowen, J.S. Welfoot, P.M. Williams, Linearized transport model for
nanofiltration: development and assessment, AICHE J. 48 (2002) 760–773.
[170] A.E. Childress, M. Elimelech, Relating nanofiltration membrane performance
to membrane charge (electrokinetic) characteristics, Environ. Sci. Technol. 34
(2000) 3710–3716.
[171] S.S. Deshmukh, A.E. Childress, Zeta potential of commercial RO membranes: in-
fluence of source water type and chemistry, Desalination 140 (2001) 87–95.
[172] Y. Shim, H.J. Lee, S. Lee, S.H. Moon, J. Cho, Effects of natural organic matter and
ionic species on membrane surface charge, Environ. Sci. Technol. 36 (2002)
3864–3871.
[173] Y. Yoon, G. Amy, J.W. Cho, N. Her, J. Pellegrino, Transport of perchlorate (ClO4-)
through NF and UF membranes, Desalination 147 (2002) 11–17.
[174] A. Braghetta, F.A. DiGiano, W.P. Ball, Nanofiltration of natural organic matter: pH
and ionic strength effects, J. Environ. Eng. ASCE 123 (1997) 628–641.
[175] S. Lee, G. Park, G. Amy, S.K. Hong, S.H. Moon, D.H. Lee, J. Cho, Determination of
membrane pore size distribution using the fractional rejection of nonionic and
charged macromolecules, J. Membr. Sci. 201 (2002) 191–201.
[176] J.Y. Hu, S.L. Ong, J.H. Shan, J.B. Kang, W.J. Ng, Treatability of organic fractions
derived from secondary effluent by reverse osmosis membrane, Water Res. 37
(2003) 4801–4809.
[177] A.I. Schafer, R. Mauch, T.D. Waite, A.G. Fane, Charge effects in the fractionation
of natural organics using ultrafiltration, Environ. Sci. Technol. 36 (2002)
2572–2580.
[178] H. Ozaki, H.F. Li, Rejection of organic compounds by ultra-low pressure reverse
osmosis membrane, Water Res. 36 (2002) 123–130.
[179] P. Berg, G. Hagmeyer, R. Gimbel, Removal of pesticides and other micropollutants
by nanofiltration, Desalination 113 (1997) 205–208.
[180] S.H. Yoon, C.H. Lee, K.J. Kim, A.G. Fane, Effect of calcium ion on the fouling of
nanofilter by humic acid in drinking water production, Water Res. 32 (1998)
2180–2186.
[181] V. Freger, T.C. Arnot, J.A. Howell, Separation of concentrated organic/inorganic
salt mixtures by nanofiltration, J. Membr. Sci. 178 (2000) 185–193.
[182] R. Boussahel, A. Montiel, M. Baudu, Effects of organic and inorganic matter on
pesticide rejection by nanofiltration, Desalination 145 (2002) 109–114.
[183] B. Van der Bruggen, M. Manttari, M. Nystrom, Drawbacks of applying
nanofiltration and how to avoid them: a review, Sep. Purif. Technol. 63 (2008)
251–263.
[184] A. Al-Amoudi, R.W. Lovitt, Fouling strategies and the cleaning system of NF
membranes and factors affecting cleaning efficiency, J. Membr. Sci. 303 (2007)
6–28.
[185] S.K. Hong, M. Elimelech, Chemical and physical aspects of natural organic matter
(NOM) fouling of nanofiltration membranes, J. Membr. Sci. 132 (1997) 159–181.
[186] S.Y. Cheng, D.L. Oatley, P.M. Williams, C.J. Wright, Positively charged nano-
filtration membranes: review of current fabrication methods and introduction
of a novel approach, Adv. Colloid Interface Sci. 164 (2011) 12–20.
[187] K. Kato, E. Uchida, E.T. Kang, Y. Uyama, Y. Ikada, Polymer surface with graft
chains, Prog. Polym. Sci. 28 (2003) 209–259.
[188] R.H. Du, J.S. Zhao, Properties of poly (N, N-dimethylaminoethyl methacrylate)/
polysulfone positively charged composite nanofiltration membrane, J. Membr.
Sci. 239 (2004) 183–188.
[189] R.H. Huang, G.H. Chen, M.K. Sun, Y.M. Hu, C.J. Gao, Studies on nanofiltration
membrane formed by diisocyanate cross-linking of quaternized chitosan on
poly (acrylonitrile) (PAN) support, J. Membr. Sci. 286 (2006) 237–244.
[190] M. Elimelech, X.H. Zhu, A.E. Childress, S.K. Hong, Role of membrane surface mor-
phology in colloidal fouling of cellulose acetate and composite aromatic polyam-
ide reverse osmosis membranes, J. Membr. Sci. 127 (1997) 101–109.
 B.S. Lalia et al. / Desalination 326 (2013) 77–95
[191] M.N. Abu Seman, M. Khayet, N. Hilal, Development of antifouling properties and
performance of nanofiltration membranes modified by interfacial polymerisa-
tion, Desalination 273 (2011) 36–47.
[192] W.R. Bowen, T.A. Doneva, Atomic force microscopy studies of membranes:
effect of surface roughness on double-layer interactions and particle adhesion,
J. Colloid Interface Sci. 229 (2000) 544–549.
[193] K. Boussu, A. Belpaire, A. Volodin, C. Van Haesendonck, P. Van der Meeren, C.
Vandecasteele, B. Van der Bruggen, Influence of membrane and colloid characteris-
tics on fouling of nanofiltration membranes, J. Membr. Sci. 289 (2007) 220–230.
[194] N. Park, B. Kwon, I.S. Kim, J.W. Cho, Biofouling potential of various NF membranes
with respect to bacteria and their soluble microbial products (SMP): characteriza-
tions, flux decline, and transport parameters, J. Membr. Sci. 258 (2005) 43–54.
[195] S.Y. Kwak, D.W. Ihm, Use of atomic force microscopy and solid-state NMR spec-
troscopy to characterize structure–property–performance correlation in high-
flux reverse osmosis (RO) membranes, J. Membr. Sci. 158 (1999) 143–153.
[196] D.F. Stamatialis, C.R. Dias, M.N. de Pinho, Atomic force microscopy of dense and
asymmetric cellulose-based membranes, J. Membr. Sci. 160 (1999) 235–242.
95
[197] S.S. Madaeni, The effect of surface characteristics on RO membrane perfor-
mance, Desalination 139 (2001) 371.
[198] S. Al-Jeshi, A. Neville, An investigation into the relationship between flux and
roughness on RO membranes using scanning probe microscopy, Desalination
189 (2006) 221–228.
[199] G.Z. Ramon, E.M.V. Hoek, Transport through composite membranes, part 2: im-
pacts of roughness on permeability and fouling, J. Membr. Sci. 425 (2013) 141–148.
[200] X. Jin, X.F. Huang, E.M.V. Hoek, Role of specific ion interactions in seawater RO
membrane fouling by alginic acid, Environ. Sci. Technol. 43 (2009) 3580–3587.
[201] C.Y. Tang, Q.S. Fu, C.S. Criddle, J.O. Leckie, Effect of flux (transmembrane pres-
sure) and membrane properties on fouling and rejection of reverse osmosis
and nanofiltration membranes treating perfluorooctane sulfonate containing
wastewater, Environ. Sci. Technol. 41 (2007) 2008–2014.
[202] C.Y. Tang, Y.N. Kwon, J.O. Leckie, The role of foulant-foulant electrostatic interac-
tion on limiting flux for RO and NF membranes during humic acid fouling—
theoretical basis, experimental evidence, and AFM interaction force measure-
ment, J. Membr. Sci. 326 (2009) 526–532.