Review Membrane Fabrication

Desalination 326 (2013) 7795
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
b
Masdar Institute of Science and Technology, P.O. Box 54224, Abu Dhabi, United Arab Emirates
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
Structureproperty relationship of membranes
Structure parameters affect the membrane performance.
a r t i c l e
i n f o
Article history:
Received 18 April 2013
Received in revised form 18 June 2013
Accepted 20 June 2013
Available online 16 August 2013
Keywords:
Polymer membranes
Membrane fabrication
Porous structure
Membrane performance
a b s t r a c t
In this review, polymeric membrane fabrication techniques for pressure driven membrane processes and
membrane distillation are discussed. The fabrication technique, properties of the fabricated membranes
and performance in water desalination are related. Important parameters which affect the membrane performance such as crystallinity of the membrane based polymer, porous structure, hydrophobicity/hydrophilicity,
membrane charge and surface roughness are analyzed. Despite the fact that extensive knowledge exist
on how to tailor membrane pore structure including its surface properties and cross-section morphology
by selection of appropriate fabrication methods, there is still a challenge to produce reliable membranes
with anti-fouling properties, chemical resistance, high mechanical strength with high ux and selectivity.
To ensure progress in membrane performance, further improvements are needed of common membrane fabrication 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.
2.
3.
Introduction . . . . . . . . . . . . . . . . . . .
Membrane fabrication methods . . . . . . . . . .
2.1.
Phase inversion . . . . . . . . . . . . . . .
2.1.1.
Immersion precipitation . . . . . .
2.1.2.
Evaporation-induced phase separation
2.2.
Interfacial polymerization . . . . . . . . . .
2.3.
Stretching . . . . . . . . . . . . . . . . .
2.4.
Track-etching . . . . . . . . . . . . . . .
2.5.
Electrospinning . . . . . . . . . . . . . . .
Structurepropertyperformance relationship . . . .
3.1.
Crystallinity of the polymer . . . . . . . . .
3.2.
Pore structure . . . . . . . . . . . . . . .
3.3.
Surface properties . . . . . . . . . . . . .
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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
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B.S. Lalia et al. / Desalination 326 (2013) 7795
3.3.1.
3.3.2.
3.3.3.
4.
Conclusions .
List of
of abbreviations
abbreviations
List
References . . . .
Hydrophilichydrophobic properties
Surface charge . . . . . . . . . .
Surface roughness . . . . . . . .
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membrane surface
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1. Introduction
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88
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90
91
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92
manner from a liquid to a solid state [4]. This transformation can be

accomplished in several ways [5], namely:
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 efciency 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 microltration
(MF), ultraltration (UF), nanoltration (NF), reverse osmosis (RO) and
membrane distillation (MD) [1]. UF and MF are well-developed techniques used for water treatment, whereas RO is widely used for water
desalination and purication. 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 determine the technological and economical efciency of the aforementioned
technologies; membrane improvement can greatly affect the performance 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 preparation of polymeric membranes are summarized in Table 1. Details of
the fabrication techniques process and the material structural characteristics will be discussed in the subsequent sections.
In this article, the recent development of polymeric membrane materials 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 membranes 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 membranes 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
(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 solution 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 morphologies [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 ux = J2)
whereas the non-solvent will diffuse into the cast lm (at a ux = 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 lm nally is obtained with an asymmetric structure. Usually at J2 J1 skin UF membranes with pore size of
10300 are obtained, while at J2 = J1 mainly MF membranes with
pore size of 0.20.5 m are fabricated.
For membrane technologies, the development of the rst high-ux
anisotropic acetate cellulose (CA) RO membranes via immersion precipitation by Loeb and Sourirajan [10] was one of the most critical breakthroughs in desalination. Today, extensive knowledge exists on how
to tailor the membrane's pore structure including its cross-section
Nanofiltration
Microfiltration
Ultrafiltration
Membrane
distillation
Reverse osmosis
0.1nm
1nm
10nm
100nm
1
m
Fig. 1. Average pore size of the membranes used in different membrane processes.
10m
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
Aromatic polyamide
Polypiperzine
Polybenziimidazoline
Polyamides
Polysulfones
Polyols
Polyphenols
Polyacrylonitrile (PAN)
Polyethersulfone (PES)
Polysulfone (PS)
Polyethersulfone (PES)
Poly(phthazine ether sulfone ketone) (PPESK)
Poly(vinyl butyral)
Polyvinylidene uoride (PVDF)
PVDF
Poly(tetrauorethylene) (PTFE)
Polypropylene (PP)
Polyethylene (PE)
PES
Polyetheretherketone (PEEK)
PTFE
PVDF
Phase inversion
Solution casting
35
Interfacial polymerization
Layer-by-layer deposition
Phase inversion
0.0010.01 m
Phase inversion
Solution wet-spinning
0.001 0.1 m
Phase inversion
Stretching
Track-etching
0.110 m
Phase inversion
Stretching
Electrospinning
0.11 m
NF
UF
MF
MD
morphology by the selection of polymer, solvents and non-solvents,

additives, precipitation time, bath temperature and other parameters
during immersion precipitation [1117]. For example, different casting
conditions and post-treatments were proposed to improve the water
ux and salt rejection of the CA membranes [1824]. 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 concentration 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 tendency to form sponge-like structures is enhanced. The UF membranes
are obtained within a range of polymer concentration of 1220 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 immersion in the non-solvent water and this produces anisotropic membranes 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))) additives to casting solution are often used [29,30]. An additive can function 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 [3135].
Fontananova et al. [32] found that LiCl addition in the PVDF/
dimethylacetamide dope increases ux of the casted membranes at
low LiCl concentration of 2.5 wt.%, but it suppressed macrovoid formation at a high concentration of 7.5% LiCl and resulted in a decrease
of the membrane permeation ux. 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 concentration in the PAA/N-methyl-2-pyrrolidone system, the solution
Table 2
Main polymers used in membrane formation via immersion precipitation [2528].
Polymer
Advantages
Disadvantages
CA
Hydrophilicity
Flexibility in fabrication
Low cost
Low thermal resistance

(b30 C)
Low chemical resistance,
pH range (28)
Poor resistance to chlorine
Low operating pressure limits
Hydrophobicity
High thermal resistance

(up to 75 C)
Wide pH tolerances (113)
Good chlorine resistance
Flexibility in membrane
fabrication (wide range
of pore size)
High mechanical characteristics
PVDF
High mechanical strength
Hydrophobicity
and chemical resistance
High thermal stability (up to 75 C)
Polyamide Wide pH tolerance
Poor chlorine resistance
(PA)
High thermal stability
High mechanical properties
PS and
PES
Fig. 2. Schematic representation of a lm/bath interface: J1 is the non-solvent ux and J2 the

solvent ux. X is the position of the interface between the lm and the coagulation bath, x is
the spatial position coordinate normal to the membrane surface, y = x X(t) is the
position coordinate that moves with the interface. m is the position coordinate in the
polymer-xed frame of reference, and M is a support [9].
80
viscosity can be raised to the point where macrovoid formation is

hindered and development of a nely 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 solvent, which was supported by the signicant 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 precipitation (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 [3335].
Saljoughi et al. [36] reported that an increase of PVP concentration
in the cast lm from 0 to 1.5 wt.% resulted in the facilitation of
macrovoid formation in the membrane sub-layer, which increased
pure water ux. 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 ux, where the macrovoid had been suppressed gradually. Wang et al. [37] showed that the PVP-added PES membrane has a
higher water ux 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 signicant 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 lm 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 ux of the prepared
membranes at different coagulation bath temperatures (0 and 25 C).
Increasing PEG concentration in the cast lm results in the facilitation
of macrovoid formation in the membrane sub-layer, which increases
ux 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 modier 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 PESadditive interaction. Ultraltration
experiments also demonstrated that more than 70% of the initial
water ux 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 molecules 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 (170 nm) via the phase-inversion process by dispersing 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 signicantly 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 increased water permeate uxes 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 membranes showed typical asymmetric morphology with nger-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(ac) shows a log-normal pore size distributions for the membranes with TiO2 content of 12 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 (5070 nm) caused by the nanoparticle
aggregate phenomenon, which leads to a bimodal pore distribution
(Fig. 4d). The mean pore radius of the membrane with 12 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 ux through
such membranes can be increased signicantly. It was also shown that
the addition of TiO2 nanoparticles causes the decrease of contact angle
from 85 for pure PS membrane to 4152 for TiO2/PS membranes, indicating that TiO2 addition enhances the hydrophilicity of membrane as a
few of hydrophilic TiO2 nanoparticles adsorb and stick on the membrane 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 nanoparticles released from the modied 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 prepare membranes for various applications. At the rst stage, a sufciently
viscous polymer solution is prepared in a solvent (or in binary/ternary
mixture of solvents) and a non-solvent. Then a prepared polymer solution is casted on a at porous substrate using a doctor blade technique
[50]. When the volatile solvent evaporates from the casted solution, a
thin polymer lm is formed on the porous support. The morphology
of the solution casted lms 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
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].
81
82
Fig. 5. SEM images of the surface morphologies of the porous silicon rubber membranes prepared at different liquid parafn concentrations (a) 10, (b) 15, (c) 20, (d) 25, (e) 30 and
(f) 40 wt.% [53].
lms using PEG used as pore former. The pore size of the membranes
was in the 512 m 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 parafn.
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-lm composite (TFC) RO and NF
membranes. The rst interfacially polymerized TFC membranes
were developed by Cadotte et al. [54] and represented a breakthrough in membrane performance for RO applications [55]. The original 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 ux [55].
Due to the signicant 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 developed [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 [5760].
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 preparation 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 advantageous to the improvement of antifouling property of the membranes.
Fig. 6. Preparation of thin lm PA membrane from m-phenylenediamine (MPD) and trimesoyl chloride (TMC) via IP [56].
For example, Li et al. [65] synthesized two novel tri- and tetrafunctional biphenyl acid chloride: 3,4,5-biphenyl triacyl chloride
and 3,3,5,5-biphenyl tetraacyl chloride, which were then used to prepare TFC RO membranes with MPD. Similarly, Liu et al. [66] presented
a novel RO composite membrane prepared from 5-isocyanatoisophthaloyl 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 modiers into TMC or MPD solutions. The modiers can participate 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 molecular weight 200 and 1000 Da into organic phase containing TMC to incorporate in situ hydrophilic surface modifying macromolecules. The
prepared membranes, which exhibited signicantly 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 ux
decline was reduced signicantly after incorporating organic modiers 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 modication of PA layer through the use of diamine
moieties could greatly enhance the chlorine resistance of the membrane 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 incorporation of ester linkage increased the oxidation resistance of the
membrane and this signicantly 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 producing PE and PP based membranes for use in energy storage devices
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 [7678]. 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, rst cold
stretching followed by the hot stretching. Cold stretching is used to
nucleate the micropores in the precursor lm followed by the hot
stretching to increase/control the nal 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 nal 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 [7981]. They found that molecular
weight of PP is a key parameter to control the structure of the membranes 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
lm [80]. Addition of long branched PP improved the lamellae thickness for the blend and increased the porosity of the blend membrane.
They also prepared porous membranes using PVDF of different melt
ow 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 biaxially stretched membranes (Fig. 7) showed the effect of stretching on
the brils connecting the island like fraction of the lm.
Tabatabaei et al. investigated the effect of blending (different molecular 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 distribution of pores. The addition of high molecular weight PP does not signicantly inuence the mechanical properties of the membranes. Kim
et al. studied the inuence of annealing on crystallite size and crystallinity of precursor PP hollow bers before the stretching process [84].
Un-annealed melt spun hollow bers does not form pores upon hot
stretching. Pre-annealing of the precursor PP hollow bers is found
to be essential for the formation of porous structure.
2.4. Track-etching
In this technique, a nonporous polymeric lm is irradiated with
energetic heavy ions leading to the formation of linear damaged
tracks across the irradiated polymeric lm. The schematic of single
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 rst stretching operation at the condition of (a) [82].
84
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 11010 cm2 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 information on the formation of particle tracks, track production mechanism, 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 cm2
for 50 nm and 2 107 cm2 for 1 m) [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 membranes 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)
lms irradiated by ssion fragments obtained from thermal neutron
ssion 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 rst bombarded the polyimide lms 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 lms bombarded with the lighter ions [92].
Starosta et al. irradiated PET lms with heavy ion beams obtained
generated by cyclotron and chemically etched with NaOH solution.
The pore size was obtained in 0.10.5 m [93]. In the above discussion, 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 uorinated
polymer viz. PVDF and its copolymers [94]. However, PVDF's resistance 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 ltration and
desalination [9597]. A high potential is applied between the polymer
solution droplet and the grounded collector. When the electrostatic
potential becomes sufciently 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 brous membranes are controllable aspect ratios (aspect ratio = L/d; Llength of the ber and
ddiameter of the ber) and morphology of the nano/microbers,
which is achieved by varying the solution viscosity, environmental

conditions, applied electric potential and the ow rate of the solution
[98]. Porosity, pore size distribution, hydrophobicity and surface morphology of the electrospun mats are controlled by the ber diameter
and its morphology [96]. Due to the precise control on the ber size,
shape and morphology electrospun brous membranes have been
used for ltration and MD processes [97,99104]. Zong et al. investigated the effect of polymer solution viscosity, applied potential
strength, solution feed rate and ionic salt addition (to improve the
conductivity of solution) on the ber diameter and nanostructured
morphology [105]. Minimum potential difference of 20 kV was required to form a stable jet using 30 wt.% solution of poly(D,L-lactic
acid) in dimethyl formamide. The electrospun bers 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
bers. Viscosity of the polymer solution also plays an important role
to form a beaded free smooth bers, a minimum viscosity of solution
is needed to form smooth bers which was 35 wt.% poly(D,L-lactic
acid) in dimethyl formamide in the present case. However, the minimum 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 bers,
bers obtained from PDLA solution with 1 wt.% NaCl possessed the
smallest average ber 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 bers. 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. acetone, dimethyl formamide, methylene chloride, acrylonitrile, nitromethane 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 ber size of the polystyrene (PS) electrospun bers
[107]. They found that ber diameter of the PS bers, electrospun
from 30 wt.% PS/DMF solution, increased from 0.9 m to 3.93 m
with an increase in relative humidity from 11 to 43%. The relative
humidity affects the solidication rate of electrospun bers, the bers
electrospun above 24 %RH had smooth surface. Below 24 %RH
the bers have wrinkled surface. Due to the formation of wrinkles
at low RH, the diameter of the bers becomes smaller.
Lin et al. studied the formation of micro- and nanoporous structures of the PS ber by varying the solvent composition and solution
concentration of PS solution [108]. The bers electrospun from
30 wt.% PS solution in THF showed ribbon like structure with densely
packed nanopores. With the addition of DMF in THF, nanopores disappear and ber surface becomes smooth. The decrease in concentration of PS in DMF/THF resulted in the formation of beaded structure of
nanobers.
Fig. 8. Schematic showing single ion-irradiation setup used to fabricate track etched membrane [90].
85
Fig. 9. Schematic showing electrospinning of polymer solution.
Kaur et al. fabricated the PAN nano-brous membranes of different ber sizes by varying the concentration of PAN solution and
they found that a decrease in the ber size diameter decreases the
pore size of the microltration nano-brous membranes [109]. This
helped to improve the salt rejection of the membrane at the expense

of water ux. Further, the mean pore size, pore size distribution
and mechanical properties of the electrospun PAN membranes can
be controlled by hot pressing. Hot pressing helps to fuse the bers
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
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 nanober membranes on the hydrophobicity
and performance in direct contact membrane distillation [95]. Addition 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 nanobrous membrane [111]. Improvement in
contact angle 128 to 134 with the addition of 40 wt.% tetramethyl
orthosilicate in PVDF nanobrous membrane was observed. Further,
thermal treatment increased the surface roughness of the membrane
due to formation of silica particles by solgel reaction of tetramethyl
orthosilicate. The increase in surface roughness of the ber further
increases the contact angle to ~ 145.
3. Structurepropertyperformance relationship
Usually, the membrane performance (ux, rejection and fouling)
is strongly inuenced by membrane polymer properties, porous structure and specic membrane surface features [112114]. The most
important parameters, which affect the membrane performance, such
as crystallinity of the membrane based polymer, porous structure, hydrophobicity/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 exibility, chain interactions
and molecular weight of the polymer [115]. In general, most polymers exist in the semi-crystalline (consist of amorphous and crystalline 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 permeable membrane. The crystallites of the polymers have highly packed
structure; liquid permeates cannot penetrate inside the packed structure and the transport of liquid takes place through the amorphous
layer. Peterlin et al. studied the effect of crystallinity, spatial distribution of crystallites and fractional free volume on the sorption and
diffusion in polymers [116]. Diffusion coefcient and crystallinity of
the polymers can be described as [117]:

n
Di Di;o c =B ;
where Di,o diffusion coefcient at zero concentration, c is the fraction 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 collagen membranes and found that ltration coefcient increases when
swelling of membrane increases in the amorphous state. The behavior
is opposite for the crystalline phase, the ltration coefcient 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 reduction of permeation ux 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 ber membranes resulted in a transition from
-phase to -phase crystal structure and restricted the movement of
PVDF. This led to deterioration of transport properties of the membrane.
However, PVDFSiO2 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 lm [122,123]. Minelli et al.
investigated the effect of plasticization (glycerol as plasticizer) of
microbrillated cellulose on the water sorption, diffusion coefcient
and structure of polymer lms. 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 cellulose acetate propionate on the porosity, pure water ux and thermal
stability [125]. They found that up to 75 wt.% blending of PVDF, the
pure water ux improved. But, above 75 wt.% crystallization dominates
resulting in the reduction of ux and porosity of the membrane.
3.2. Pore structure
Water ux 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 between fabrication technique and pore structure of the membrane
helps to design a membrane for particular application. Some characteristic pore geometries of the membranes are illustrated in Fig. 11.
The simplest geometry of the membrane is characterized by parallel 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 denes the permeate ux as:
J
r 2 P
;
8 x
where J is solvent ux, is surface porosity, r is pore radius, P

is pressure difference across the membrane of thickness x, is viscosity of the solution and is the pore tortuosity.
However, few membranes follow HagenPoiseuille equation,
because of different pore geometries. Membranes prepared by phase inversion, stretching, solution casting and electrospinning have irregular
pore geometry and tortuosity. KozenyCarman modeled the relationship between ux and geometrical parameters of the membrane pores:
J
3
P
;
KS 12 x
2
where, is the volume fraction of pores, P is pressure difference across

the membrane of thickness x, is viscosity of the solution, K is
KozenyCarman constant (depends on the shape of the pores and tortuosity) and S is the internal surface area of the membrane pores.
In the phase inversion technique, the composition of the membrane 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 ber membranes [30,129131]. They found that hot water
(a)
(b)
(c)
(d)
87
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 modied PES phase
inversion membranes [127], (c) track etched PC membrane irradiated with Kr ions [128] and (d) electrospun PVDF-co-hexauoropropylene 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 shrinkage 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 ux 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 ber membranes were reported
by Matsuura and co-workers [132,133]. It was observed that increasing PEI concentration in the spinning solution decreases the mean
pore size, effective surface porosity and formed the nger 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 modied
the hydrophobicity of the PEI hollow ber membranes by introducing
surface modifying macromolecules. Modied-PEI membranes have
higher mean pore size, permeation rate, inner and outer surface contact 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
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 membrane 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 cellulose acetate/acetone/water solution using video-microscopy owvisualization. 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
uid 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 ux and mechanical
properties of the membranes [137]. The increase in PAN concentration from 10 to 22 wt.% reduces the pore size of the membranes
from 5.3 to 0.8 m and correlated this with the viscosity of the
solution. The membranes have cellular like pores for mixed diluent
(glycerol and dimethylsulfone) with 2030 wt.% glycerol, whereas
needle like pores for 1015 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
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 tetrahydrofuran (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 concentration 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 modied) on the membrane performance and its structural and mechanical properties [139]. Addition
of mechanically modied TiO2 increases the number of microvoids in
the membrane whereas chemically and modied TiO2 nanoparticles
lead to elongation of nger like microvoids. These structural modications with incorporation of TiO2 nanoparticles in the membrane improve the pore size, porosity and hydrophilicity of the membrane
which results in an improvement of water ux through the modied
membrane.
Han et al. prepared the ultraltration 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 membrane. Incorporation of CMCA and PEG caused the formation of more
pores and macrovoids beneath the skin layer. Addition of CMCA decreases the pure water contact angle on the surface of the membrane
and improved the pure water ux through the membrane.
3.3. Surface properties
3.3.1. Hydrophilichydrophobic properties of membrane surface
As known, the common-evaluation approach for hydrophilichydrophobic properties of membrane is based on evaluation of a contact
angle formed between the liquidgas tangent and membraneliquid
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 characterized 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 applications. 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 contact angle. Chang et al. [143] reported that the steroid estrone was
highly rejected with MF hollow bers due to adsorption mechanism
despite of a wide pore size of the membrane. Estrone rejection
decreases with ltration 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 sorption and rejection decreased with time [114,144148].
Kiso et al. [148] reported that the rejection of hydrophobic molecules by NF membranes increased linearly with afnity of the solute
for the membrane as expressed through the octanolwater distribution coefcient (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 bonding 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 ux decline. It was also
shown [149,151] that polar compounds with sizes similar to membrane
pore diameters caused the greatest amount of ux decline through pore
blocking or adsorption within the pores.
Apart from membrane rejection, hydrophilichydrophobic properties
of the polymer membrane have a crucial inuence on its anti-fouling
property and permeate ux [152,153]. It has been well documented
that membranes with hydrophilic surfaces are less susceptible to fouling
with organic substances, microorganisms, and charged inorganic particles [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 ltration of bovine serum albumin
solution the relative ux decreases, which correlates with the membrane 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 ux of the PVA/PVDF membrane was 14% higher than that of the unmodied PVDF membrane
after 4 h of ltration and 95% higher after 18 h of ltration (Fig. 12).
As can be seen in Fig. 12, the ux of the modied membrane reached
a plateau with increasing operating time, while the ux for the
unmodied 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
modied membrane by alkaline cleaning. The higher performance of
the modied membrane was related to the increasing in hydrophilicity 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 membrane surface is a spontaneous process with increasing entropy and
therefore foulant molecules have a tendency to adsorb onto membrane surface and dominate the boundary layer. In contrast, the
membrane with the hydrophilic layer possesses a high surface tension 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 difcult therefore for hydrophobic
solutes to approach the water boundary and break the orderly structure 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, microorganisms and organic pollutants. For example, it was found that the improvement on hydrophilicity can favor enhancing the permeate ux
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 membrane closely related with its surface features, including functional
groups, zeta potential, and surface roughness [159,160]. It was demonstrated that the increase of the density of surface hydrophilic-group,
such as -OH, and -NH2, is favorable for improving the membrane hydrophilicity [161,162]. Tang et al. [163] reported that the contact angles
89
Fig. 12. Variation of the normalized uxes (Grand River water ux/clean water ux) between base PVDF and modied 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 macromolecules 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 solidliquid 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 surrounding water molecules by Coulombic attraction with the waternegative 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 rejection mechanism [112,167170]. These interactions depend on the
membrane charge which is usually quantied by zeta potential measurements [112]. The membrane surface of RO, NF and UF membranes often carries a negative charge to increase the rejection of
dissolved salts and minimize the adsorption of negatively charged organic 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 electrostatic 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
that while the rejection of uncharged urea decreased slightly from

35 to 28%, the rejection of acetic acid increased from 32% in the neutral 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 membrane surface repelling the negatively charged ions of acetic acid.
On the other hand, the effect of membrane surface charge on
membrane pore structure, permeate ux and the rejection of uncharged organics at various pH is somewhat contradictory. It has
been reported that the rejection of uncharged solutes decreased,
while permeate ux increased at high pH values (810) due to an increase in pore size of a membrane caused by the electrostatic repulsion between the functional groups within the membrane [179].
Some studies have found small dependence of the rejection of
uncharged organics and permeate ux 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 membrane 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 electrostatic 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 benecial
effect on separation proteins around neutral pH, because most of proteins 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 ux 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 benecial [186]. These membranes may be used for the recovery of valuable cationic macromolecules in biotechnology. Similar to
the negatively charged surface, the positively charged membrane surfaces exhibited electrochemical repulsion against positively charged
90
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, uxes for commercial RO (Hydranautics LFC-1,
Trisep X-20) and NF (Dow-FilmTec NF-70, Osmonics HL) membranes
during ltration 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 accumulation 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 valley clogging which causes more severe ux 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 ltration 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 membrane surface roughness signicantly reduced electrostatic repulsion
between the colloid and the surface, and the valley regions experienced a greater adhesion force.
On the other hand, Boussu et al. [193] suggested that while colloidal fouling was affected by both membrane roughness and hydrophobicity, membrane hydrophobicity seems to play a more signicant
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 authors attributed the greater anti-fouling tendency to the large repulsive acidbase interaction for the more hydrophilic poly(piperazine)
membranes.
While results on membrane fouling depending on surface roughness seem fairly consistent (i.e., rougher membranes foul more
quickly and are harder to clean), contradictory ndings are reported
on effect of surface roughness on membrane ux: higher surface roughness can mean higher ux, lower ux or have no effect on ux. Hirose
et al. [113] suggested an approximately linear relationship between
membrane surface roughness and ux for cross-linked aromatic polyamide 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 ux decline for the ltration of 0.05 M NaCl solution, which contained
200 mg/L silica particles (0.10 m). 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 nd a linear relationship between
membrane surface roughness and ux in ltration tests with
thin lm polyamide RO membranes. The performance tests were carried out with 0.2% NaCl solution at 15 bar and 25 C. However, the
roughest membrane did have the highest ux. On the other hand,
Stamatialis et al. [196] showed that the lower surface roughness of
CA and cellulose acetate butyrate membranes the lower the ux and
the higher the rejection during ltration of 3500 ppm NaCl solution
at operating pressure of 40 bar. However, no explanation of these
ndings has been provided. Madaeni [197] also found that the rougher 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 correlation between surface roughness and ux 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 lms and the underlying
porous support membrane. They showed that: i) permeability increases with surface roughness if the roughness is created while producing thin regions in the coating lm, essentially reducing the base
lm thickness; however, when roughness is formed on top of an
unvarying base lm thickness, the permeability of the lm decreases
with increased roughness; and ii) when surface roughness comes at
the expense of base lm thickness, the thinner regions (valleys)
present locally higher ux (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 xed 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 hydrophilic surface with no carboxylic moieties is presumably the best
membrane option. In their study, the membrane with a hydrophilic
PVA coating showed signicantly 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 signicant 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 fabrication of polymer membrane, the membranes properties and performance 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 interpret 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-specic parameters. For example, the formation of membrane made by the immersion 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 conditions, casting thickness, type of membrane support material, drying
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
Interfacial polymerization
Stretching
Track-etching
Electrospinning
H
H
M
L
M
H
H
M
H
M
L
L
M
H
M
H
L
H
L
H
M
H
L
L
L
M
H
L
M
M
H
L
M
L
H
H
L
L
L
M
H
H
L
L
L
H High; M Medium, L Low.
conditions, etc. Additionally many membrane properties may be

inuenced simultaneously with the same fabrication process.
It can be seen in Table 3 that membrane properties and performance can be tuned to larger extend through the discussed
membrane fabrication methods. Phase inversion and interfacial polymerization are probably the most versatile and cost effective membrane fabrication techniques for preparation of polymer membranes
in a wide range of pore sizes (from RO to MF membranes) with various hydrophilic/hydrophobic and charged properties at high values
of average porosity. However in many cases the width of pore size
distribution for phase inversion membranes should be improved to
provide better retention properties. The additional advantages of
the interfacial polymerization include the possibility of tuning independently the properties of skin/support layers and a low surface
roughness of the prepared membranes, which are of great importance for development of low fouling TFC polymer membranes for
pressure-driven membrane processes. Stretching is a simple and
low cost method for fabrication of highly porous hydrophobic membranes for MF and MD, while these membranes are still prone to
organic and (bio) colloidal fouling. The track-etched polymer membranes are usually in a MF range of pore sizes with low surface roughness and their unique futures are practically ideal cylindrical shaped
pores and a very sharp pore size distribution. However because of
low surface porosity, the membrane uxes are rather low. The other
drawback of these membranes is high cost, obviously, due to technical complexity of their fabrication. With respect to electrospinning,
it is a very promising method for preparation of highly productive
hydrophobic membranes for MF and MD but is in need of further development in terms of pore size distribution, antifouling properties,
cost reduction and fabrication on a large scale.
4. Conclusions
In this review, relationships between the synthesis of polymer
membranes, their structure, surface properties and performance
were discussed. It was shown that to date remarkable progress has
been made in the fabrications of membranes for water treatment.
However, there is still a challenge to produce reliable membranes
with anti-fouling properties, high mechanical strength, high tolerance
on chlorine attack and minimal thickness of the membrane barrier
layer to provide a high ux. To ensure progress in these elds,
more efforts are needed for further improvement of common membrane fabrication methods as well as the development of new fabrication techniques. A comprehensive understanding between porous
structure-surface properties and the performance of membranes in
water treatment processes is crucial for further development of polymer membranes and optimization of fabrication processes. Membrane
performance (ux, rejection and fouling) is strongly inuenced by
membrane chemical composition and specic features of porous structure and the membrane surface, including hydrophobic/hydrophilic
properties, membrane charge (zeta potential), surface roughness, pore
size and pore size distribution. Despite numerous research studies
attempting to relate physico-chemical properties of membranes to
solute rejection, the role of membrane structure and surface properties

in membrane performance is still not thoroughly understood. A systematic work is still needed to clarify for example the role that membrane
morphology plays in trans-membrane transport, the effect of surface
roughness on membrane ux during membrane treatment of complex
feed solutions with organic and inorganic species, the inuence of
membrane surface charge on membrane pore structure at various pH,
or for studying foulant-membrane interactions under severe fouling
conditions. Identication of these parameters and others which can
effectively be used to predict relationships between membrane fabrication, structure, surface properties and performance could be very meaningful for further development of membrane based technologies for
water treatment.
List of abbreviations
AFM
atomic force microscopy
BSA
bovine serum albumin
CA
cellulose acetate
DMF
dimethyl formamide
HFP
hexauoropropylene
IP
interfacial polymerisation
octanolwater distribution coefcient
Kow
MD
membrane distillation
MF
microltration
MPD
m-phenylenediamine
NF
nanoltration
NMP
n-methyl-2-pyrrolidone
NOM
natural organic matter
PA
polyamide
PAA
poly(amic acid)
PAN
polyacrylonitrile
PC
polycarbonate
PE
polyethylene
PEEK
polyetheretherketone
PEG
poly(ethylene glycol)
PES
polyethersulfone
PET
polyethylene terephthalate
Pluronic poly(ethylene oxide)-b-poly(propylene
(ethylene oxide)
PP
polypropylene
PPESK
poly(phthazine ether sulfone ketone)
PS
polysulfone
PTFE
` poly(tetrauorethylene)
PVA
polyvinyl alcohol
PVAc
polyvinyl acetate
PVDF
polyvillidene uoride
PVP
polyvinyl pyrrolidone
RO
reverse osmosis
TFC
thin lm composite
TFE
tetrauorethylene
THF
tetrahydrofurane
TMC
trimesoyl chloride
UF
ultraltration
oxide)-b-poly
92
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Review Membrane Fabrication

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Desalination 326 (2013) 7795

Contents lists available at ScienceDirect

A review on membrane fabrication: Structure, properties and

Corresponding author. Tel.: +971 28109152.

B.S. Lalia et al. / Desalination 326 (2013) 7795

manner from a liquid to a solid state [4]. This transformation can be

According to the world population clock, the population exceeds

(a) Immersion precipitation. The polymer solution is immersed in

B.S. Lalia et al. / Desalination 326 (2013) 7795

Polymers used for membrane fabrication

Average pore size of the membrane

morphology by the selection of polymer, solvents and non-solvents,

casting. An aprotic polar solvent such as N-methyl-2-pyrrolidone,

Low thermal resistance

High thermal resistance

Fig. 2. Schematic representation of a lm/bath interface: J1 is the non-solvent ux and J2 the

B.S. Lalia et al. / Desalination 326 (2013) 7795

viscosity can be raised to the point where macrovoid formation is

have with the surrounding polymer matrix [45]. A comprehensive

B.S. Lalia et al. / Desalination 326 (2013) 7795

B.S. Lalia et al. / Desalination 326 (2013) 7795

2.2. Interfacial polymerization

rejection than that of an integrally-skinned asymmetric cellulose

B.S. Lalia et al. / Desalination 326 (2013) 7795

[75]. This is a solvent free technique, in which the polymer is heated

B.S. Lalia et al. / Desalination 326 (2013) 7795

ion-irradiation setup is shown in Fig. 8. This technique is famous for

which is achieved by varying the solution viscosity, environmental

B.S. Lalia et al. / Desalination 326 (2013) 7795

Fig. 9. Schematic showing electrospinning of polymer solution.

helped to improve the salt rejection of the membrane at the expense

B.S. Lalia et al. / Desalination 326 (2013) 7795

together and reduce the thickness of the electrospun membrane

size and free volume hole density resulting in improvement in water

where J is solvent ux, is surface porosity, r is pore radius, P

where, is the volume fraction of pores, P is pressure difference across

B.S. Lalia et al. / Desalination 326 (2013) 7795

treatment of cellulose, CA and cellulose triacetate membranes lead

solution preparation, and studied the formation of highly dense

B.S. Lalia et al. / Desalination 326 (2013) 7795

Zhao et al. prepared asymmetric PVDF membranes using solution

B.S. Lalia et al. / Desalination 326 (2013) 7795

of PVA coated RO membranes are smaller than those of uncoated

that while the rejection of uncharged urea decreased slightly from

B.S. Lalia et al. / Desalination 326 (2013) 7795

relationship was attributed to surface unevenness of the RO membrane

B.S. Lalia et al. / Desalination 326 (2013) 7795

H High; M Medium, L Low.

conditions, etc. Additionally many membrane properties may be

solute rejection, the role of membrane structure and surface properties

B.S. Lalia et al. / Desalination 326 (2013) 7795

B.S. Lalia et al. / Desalination 326 (2013) 7795

B.S. Lalia et al. / Desalination 326 (2013) 7795

B.S. Lalia et al. / Desalination 326 (2013) 7795

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