Morphology Control of Polysulfone Membranes in Filtration
Processes: a Critical Review
Amira Abdelrasoul[1],*, Huu Doan[1], Ali Lohi[1], Chil-Hung Cheng[1]
Abstract
Polysulfone (PSU) membranes have been widely ap-
plied in microfiltration and ultrafiltration processes
due to their excellent properties, such as chemical
inertness across the entire pH range, compressive
strength, and thermal stability. Despite these advan-
tages, the application of PSU membranes in filtra-
tion processes has often been restricted due to their
hydrophobic nature, which results in serious mem-
brane fouling and a reduced permeate flux. More-
over, PSU membranes suffer from several disadvan-
tages, including bulky structure, low binding force
between fibers, and poor mechanical properties.
The key factor in the development and application
of polymeric membranes is the control of its poly-
Keywords: Polysulfone membrane, Morphology, Pore size, Porosity, Performance, Fouling
Received: October 17, 2014; revised: November 18, 2014; accepted: November 19, 2014
DOI: 10.1002/cben.201400030
1 Introduction
Polysulfone (PSU) has numerous excellent properties, such as
chemical inertness on the entire pH range, compressive
strength, thermal stability (150–170 C), and mechanical
strength (fracture, flexure, torsion), and as such is one of the
most popular synthetic polymer materials used for the fabrica-
tion of membranes [1–2]. In the recent past, PSU membranes
have been widely applied to micro-/ultra-filtration, gas separa-
tion, pervaporation, hemodialysis, plasma separators, mem-
brane oxygenators, cell culture, and bio artificial organs [3–6].
The market share for the PSU membrane use is continuously
increasing, for instance, the PSU is the most widely used mem-
brane for CO2/CH4 separation process due to its low price,
chemical stability, and mechanical strength. The world market
for natural gas is estimated at approximately US-$ 22 billion
annually and as it keeps growing, the market for PSU mem-
brane technology will be increasing as well [7]. Compared to
cellulose acetate, PSU has lower CO2 permeability and CO2/
CH4 selectivity but higher plasticization pressure, the pressure
at which the permeability starts to increase with increasing the
penetrant concentration or pressure [7]. Plasticization pressure
becomes important in practice due to its effect on membrane
selectivity with high CO2 feed concentration or on high operat-
ing pressure [7]. Nevertheless, applications of the PSU mem-
www.ChemBioEngRev.de ª 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
meric morphology due to the significant influence
of membrane morphology on the membrane perfor-
mance. Effective techniques of controlling PSU
membrane morphology are accessed, and the effects
of the morphological control on mechanical proper-
ties, chemical stability, membrane performance, and
membrane fouling are investigated. Findings from
various individual studies were analyzed and dis-
cussed in order to provide a critical review of this
subject. The results emphasized that the membrane
pore size and surface porosity mostly governs PSU
membrane morphology, which enhances membrane
performance and reduces membrane fouling.
branes in the filtration of aqueous solutions are often limited
because of their hydrophobic nature which results in a low per-
meate flux and significant membrane fouling. Moreover, PSU
membranes suffer from a number of disadvantages, such as
bulky structure, low binding force between fibers, and poor
mechanical properties. The thermodynamic, rheological and
adsorptive properties have been found to significantly change
with its surface modification [8–9].
The surface modification and post-treatment of PSU mem-
branes has become a popular subject for discussion among re-
searchers. In particular, there are three different directions in the
process of modification and post-treatment. First, to introduce
the hydrophilic group to the surface layer by coating, adsorp-
tion, plasma treatment, pH treatment, and surface grafting poly-
merization, so as to increase the hydrophilicity of PSU mem-
branes [10–13]. Second, to promote the performance of the PSU
membrane by adding the hydrophilic substance into the PSU
preparation solution to gain a hydrophilic blend membrane
—————
[1]
Dr. Amira Abdelrasoul (corresponding author), Prof. Huu Doan,
Prof. Ali Lohi, Prof. Chil-Hung Cheng
Department of Chemical Engineering, Ryerson University, 350 Vic-
toria Street, Toronto, Ontario, M5B 2K3, Canada.
E-Mail: amira.abdelrasoul@ryerson.ca
ChemBioEng Rev 2015, 2, No. 1, 22–43 22
[14–17]. Post treatment, such as heat treatment and acid treat-
ment, is the third kind of treatment adopted to control the mor-
phology of the membrane so as to improve performance of the
PSU membrane [18–23]. Morphology, structure, chemical na-
ture, chemical and thermal properties are all important charac-
teristics that should be extensively studied to improve materials
and ensure a better performance. The combination of all these
properties defines the success of a membrane [24]. The key fac-
tor in the development and application of polymeric mem-
branes is the control of its polymeric morphology. As a conse-
quence, many researchers have recently investigated the
influence of the control of membrane morphology on the mem-
brane performance [25]. Membrane pore size and membrane
porosity, governing factors of membrane morphology enhance
the membrane performance and reduce membrane fouling [26].
2 Morphological Characterization
of Membranes
2.1 Membrane Morphology Parameters
It is worth briefly noting the key membrane morphological
parameters that affect membrane characterization and per-
formance. Fig. 1 summarizes the main membrane morphology
parameters. The mean pore size and pore size distribution are
the two membrane characteristics that govern most membrane
applications [25]. Pore tortuosity is the morphological para-
meter which provides information on how far, in terms of
shape, the internal pore structure is different from an ideal cyl-
inder [27]. The symmetry and regularity parameters describe
the membrane pore distributions. The symmetry parameter
corresponds to the distribution of the pores, with respect to
number and size of the membrane cross-section, as well as in
the direction of the fluid flow. A membrane is defined as sym-
metric if the pore size distribution remains the same through-
out the membrane thickness. Alternatively, as much as it can
differ, the membrane is identified as asymmetric. Depending
on the case, it could be advantageous to have a different pore
number or size for fluid advancement. The homogeneity of
pores in the membrane, in size and number, perpendicular to
Figure 1. Membrane morphology parameters.
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the fluid flow determines the regularity. Normally, a high regu-
larity is a necessary condition of an effective membrane.
Porosity of the membrane is a crucial morphological param-
eter, which is responsible for the evaluation of the total amount
of free volume in a membrane. Other parameters to consider
are the membrane thickness and the thickness of the selective
layer. Thickness is a key parameter in membrane processes
since it influences both the membrane selectivity and the mem-
brane resistance against flux. Surface roughness is another
crucial morphological parameter because it appears to be di-
rectly related to the membrane fouling [25, 26]. Microscopic
techniques for membrane morphology characterization include
the following: scanning electron microscopy (SEM), atomic
force microscopy (AFM), confocal scanning laser microscopy
(CSLM), and transmission electron microscopy (TEM).
The two parameters which play an essential role in the evalu-
ation of the membrane performance are permeability and cut-
off. Permeability corresponds to the normalized permeate flow,
transmembrane pressure (TMP), membrane area, and the cut-
off which, by definition, corresponds to the size of the particles
that are 90 % retained by the membrane. The permeability of
the permeate is very difficult to predict due to fouling and
polarization, which can reduce the flow rate dramatically. The
selection of the cutoff of the membrane used not only depends
on the type of filtered solute but also on the transmembrane
pressure applied [28].
In our previous studies [29, 30] for uniform and non-uni-
form pore size membranes, it was determined that the pore
size, surface porosity, pore length, density of membrane pores
per unit membrane surface area, and membrane tortuosity, all
influence the mass of fouling attached to the membrane sur-
face, as well as the extent to which transmembrane pressure in-
creases due to membrane fouling. In addition, there is the im-
pact of the operating conditions as well as the solution
chemistry on fouling attachments and the membrane perform-
ance [31, 32]. The pore size distribution had a significant effect
on the mass of fouling retained by the membrane, and the in-
crease in transmembrane pressure at the same operating condi-
tions. The design of the membrane module likewise plays a
critical role. A correct design of the module can prevent stag-
nant flows inside the module (which reduces the effective
membrane area) and it can significantly increase the shear
stress on the membrane, which can aid in preventing the men-
tioned phenomena.
2.2 Synthesis Considerations of Membranes
Membranes are selective barriers which allow for the compo-
nent separation between two phases. The choice of polymer is
a key factor since it dictates the specific properties and struc-
tural parameters of the membrane. Various methods for the
preparation of PSU membranes have been described. One of
the most popular methods used is the Loeb–Sourirajan phase
inversion process. This method, which is extensively described
in [27], is based on the interaction of at least three compounds:
a polymer, a solvent, and a nonsolvent. A polymeric solution is
prepared by combining the polymer with the solvent, which is
then immersed in a coagulation bath containing the nonsol-
ChemBioEng Rev 2015, 2, No. 1, 22–43 23
vent, which, additionally, can contain also solvent or other ad-
ditives, leading to the precipitation of the polymer. A mass
transfer occurs, the solvent migrates to the nonsolvent and vice
versa, which results in the formation of the membrane after a
phase inversion process, due to the reaching of a two-phase im-
miscible region. For PSU membranes, this process can be rep-
resented in a ternary diagram of polysulfone (PSU, polymer),
dimethylformamide (DMF, solvent), and water (nonsolvent).
The final membrane morphology obtained depends on the in-
teraction of the mentioned compounds [33], the coagulation
bath temperature, the polymer concentration, etc. [27]. For a
given polymer, the best way to obtain the widest range of mem-
brane morphologies is to modify the composition of the coagu-
lation bath that includes the nonsolvent [25]. A high-interac-
tion parameter between the nonsolvent and the polymer, e.g.,
water and PSU, produces a fast mass transfer, which leads to
an asymmetric morphology structure with macrovoids. Alter-
natively, a low interaction between the nonsolvent and the
polymer, e.g., isopropanol and PSU, produces a delayed mass
transfer, which leads to a symmetric morphology structure
without macrovoids. It should also be noted that the polymer
concentration in the initial polymeric solution exhibits some
influence on the final membrane morphology [34]. Notably,
the interaction parameters between the polymer and nonsol-
vent are thermodynamic variables and, hence, control the driv-
ing force for mass transfer, which in turn controls the kinetics.
The dissolution of the polymer is governed by the free energy
of mixing for the phase inversion technique to form asymmet-
ric membranes. A negative value of the free energy change on
mixing means that the mixing process will occur spontane-
ously. Otherwise, two or more phases result from the mixing
process. Since the dissolution of a high molecular weight poly-
mer is always associated with a very small positive entropy
change, the enthalpy term is the crucial factor in determining
the sign of the Gibbs free energy change [35].
3 Methods for Morphology Control
of PSU Membranes
3.1 Heat Treatment Influence on PSU
Morphology
Relaxed heating and tension heating were the two heating
methods used to control the morphology of PSU membranes.
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Relaxed heating was accomplished by hanging the PSU mem-
brane with one point fixed in the oven. In case of the tension
heating, in order to prevent shrinkage of the membrane, two
iron clamps (50 g each) were used to hold the opposite sides of
the membrane without peeling the membrane from the alumi-
num foil. The two treatment methods of heating are shown in
Fig. 2.
Figure 2. Scheme of heat treatment [23].
Researchers investigated the effect of heat treatment at differ-
ent temperatures [23]. PSU membranes treated at 180, 185,
190, and 195 C with relaxed heating and tension heating are
shown in Fig. 3 and Fig. 4, respectively. As seen in Fig. 3, after
the relaxation heating up to 180 C, the fiber diameter slightly
increased. Raising the temperature from 180 C to 195 C, re-
sulted in the straight fiber tending to be curved, but with no
obvious change in fiber diameter. For tension heating, the fiber
surface morphology exhibited no significant difference after
heating to 175 C. Further increase in heating temperature up
to 180 C, the fiber diameter began to noticeably decline as
shown in Fig. 4. However, with the temperature continuing to
increase from 185 C to 195 C, the descending tendency be-
came less pronounced, and there was no change in the surface
morphology. It is worth briefly mentioning that decreases in
fiber diameter resulted in an increased membrane porosity. As
a consequence, PSU would have better performance at the
same operating conditions.
Comparing the difference in the distributions of fiber diame-
ter between the PSU membrane with tension heating versus re-
laxation heating, Fig. 5 illustrates that tension heating had bet-
ter results in reducing the fiber diameter. Similarly, the
Figure 3. SEM pictures of the
PSU membrane after heat treat-
ment with relaxation heating
(heating time: 3 h · 5000) [23].
ChemBioEng Rev 2015, 2, No. 1, 22–43 24
Figure 4. SEM pictures of the PSU membrane after heat treatment with tension heating (heating time: 3 h · 5000) [23].

Figure 5. Distributions of the fiber diameters of the PSU membrane with tension heating and relaxation heating [23].

membranes showed more surface porosity.

In the case of the relaxed state, the molecu-
lar chains tended to remain in a stable state
with minimum energy, while the PSU fiber
shrunk. However, due to the restrain of the
entanglement crosslink between fibers, the
shrunken fiber appeared to be curved at
the same time. On the other hand, in the
tension state, the molecular chains would
stretch and rearrange along the direction of
the external force under the effects of both
heat and tension, as the external tension
force rearranged the polymer segments. Figure 6. SEM pictures of the PSU membrane after tension heating treatment at 190 C
This resulted in an enhanced structural [23].
density of the internal fibers and a decrease
in the fiber diameter.
Time exerted a significant impact on tension heating treat- ically. As the heating continued, the arrangement of the molec-
ment on PSU morphology. The SEM images of the PSU mem- ular chain in the direction of the external force was increased,
brane treated with tension heating at 190 C for 1, 3, and 5 h while the fiber diameter gradually decreased. The decrease of
can be seen in Fig. 6. The images illustrate that the fiber diame- the fiber diameter resulted in an increase of the membrane sur-
ter decreased as the heating time increased to three hours. Al- face porosity and the pore size distribution. Once all of the mo-
ternatively, once the heating time reached five hours, there was lecular chains attained the most stable state, the microstructure
close to no change in the fiber diameter. Although molecular of fiber ceased to change, indicating that the fiber diameter
chains and segments of the fibers rearrange with the applica- would cease to fluctuate.
tion of heat, due to the inter- and intra-molecular interactions, It could be concluded that tension heating treatment at
such structural change proved to be dependent on time. At the 190 C for three hours provides the best results for morphology
initial stages of heating, the molecular segments with particular control and obtaining high surface porosity of the PSU mem-
activation energy rearranged in accordance with the direction brane. Moreover, heating treatment resulted in a chemically
of the external force order. This kept the arrangement of mole- stable membrane suitable for a variety of applications which
cules tight and regular, and changed the fiber diameter dramat- will be further discussed in Sect. 4.

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3.2 Recent Advances in the Preparation and
a) b)
Morphology Control of Polymeric Membranes

Among the methods used for the preparation of polymeric

membranes, the most popular one is the phase inversion meth-
od [36]. In this method, the phase separation and subsequent
solidification (gelation) of the cast polymer solution determines
the final membrane morphology and the associated separation
performance. There are several methods that can be used to in-
duce phase separation during membrane formation: change in
the solution temperature, the thermally induced phase separa- c) d)
tion (TIPS), exchange of solvent with nonsolvent (coagulant),
the immersion precipitation or nonsolvent-induced phase
separation (NIPS), and intake of nonsolvent vapor or the
vapor-induced phase separation (VIPS) [37, 38]. In the follow-
ing subsections, the VIPS, blending an amphiphilic additive
before VIPS, and novel morphology control techniques based
on NIPS will be critically discussed.

3.2.1 Vapor-Induced Phase Separation e) f)

A number of studies indicate that the air-gap length, in which

an air gap is interposed between the membrane and a conden-
sation surface, and ambient humidity have a strong effect on
the membrane morphology prepared by VIPS [39–42]. A par-
ticular study investigated the impact of the air gap length and
humidity on the morphology of hollow fiber PSU membranes
[43]. Polysulfone hollow fiber membranes were fabricated by a
dry/wet spinning process with N-methyl pyrrolidinone (NMP) g)
and water as solvent and coagulant, respectively [44]. The ex-
perimental setup and details of the spinning conditions are
reported in [43]. Fig. 7 depicts the morphology of the hollow-
fiber membranes fabricated by varying the length of the air gap
from 0 to 60 cm, while the relative humidity in the air gap was
kept at 30 %. The results indicate that the length of the air gap
dramatically affects the morphology near the outer surface of
hollow fibers. For instance, macrovoids were seen clearly with-
out an air gap, completely disappeared with an air gap of
10 cm, then reappeared when the air gap increased to 20 cm, Figure 7. Cross-sectional membrane morphology of the PSU
became smaller with an air gap longer than 20 cm, and finally hollow fiber prepared with an ambient relative humidity of
could no longer be seen when the gap was more than 50 cm. 30 %. Air gap: (a) 0 cm, (b) 10 cm, (c) 20 cm, (d) 30 cm, (e) 40 cm,
Complete suppression of the macrovoids near the outer surface (f) 50 cm, and (g) 60 cm [43].
first occurred when the air gap was 10 cm and occurred again
when the air gap was longer than 50 cm. humidity in the air gap shortens the air-gap length required for
The effect of the air gap length was also investigated at the the re-suppression. It is crucial to acknowledge that the mor-
relative humidity of 70 %. Shown in Fig. 8 are the morphologies phology around the inner surface of fibers is not supposed to
of PSU hollow-fiber membranes spun with the air gaps from be affected by the water vapor in the air gap because it is domi-
10 to 60 cm, when the relative humidity in the air gap was kept nated by the exchange of the polymer solvent with the bore
at 70 %. In the case of no air gap (0 cm), it should be noted that liquid, quite unlike the morphology near the outer surface
the humidity in the air gap did not affect membrane morphol- which can be affected by the water intake from the outer sur-
ogy in any visible way, since the dope had no chance to contact face of the dope.
water vapor. As expected, the trend shown in Fig. 8 is similar to
that in Fig. 7 [43]. The macrovoids occurred, disappeared, re-
appeared, and re-disappeared as the air-gap length increased 3.2.2 Blending an Amphiphilic Additive before Vapor-
from 0 to 60 cm. The major difference between Fig. 7 and Fig. 8 Induced Phase Separation
is that the air-gap length required for the re-suppression of
macrovoids is 40 cm in the case of 70 % relative humidity (rh), A PSU membrane was prepared by blending an amphiphilic
and 50 cm in the case of 30 % rh, indicating that the higher additive, such as Pluronic F127 or 3-N,N-dimethylmyristylam-

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 a) b)
d) e)
Figure 8. Cross-sectional membrane morphology of the PSU hollow fiber prepared with an ambient relative humidity of 70 %. Air gap:
(a) 10 cm, (b) 20 cm, (c) 30 cm, (d) 40 cm, (e) 50 cm, and (f) 60 cm [43].
monio propane-sulfonate (DMMSAPS), with PSU before in-
ducing the phase separation of the solution [45]. The additive
affected both the membrane morphology and the surface
chemical composition. Pluronic F127 and DMMSAPS tended
to increase the porosity of the membranes. Fig. 9 depicts the
effect of Pluronic F127 concentration on the PSU morphology.
PSU membranes formed from solutions containing low Plur-
onic F127 contents (< 3 wt%) show the appearance of small
pores randomly distributed on the surfaces, as illustrated in
Fig. 9 b [45]. However, for membranes prepared using a higher
additive content of 5 wt %, SEM observations indicated a signif-
icantly more porous surface, suggesting that the additives act as
a pore former, as presented in Fig. 9 d [45]. This particular
a) b)
c) d)
Figure 9. SEM images of PSU with different F127 concentration
(a) 0 %, (b) 1 %, (c) 3 %, (d) 5 % [45].
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c)
f)
phenomenon was already observed by Zhao et al. in the pre-
paration of polysulfone membranes by liquid-induced phase
separation processes using Pluronic F127 as a pore former
[46]. In this reported study, the researchers mentioned that the
addition of Pluronic F127 was a key factor in influencing the
final membrane structure. They also reported a substantial in-
crease in water permeability with increasing the additive con-
centration. The results of their experiments had effectually
shown that the pores in the skin layer were enlarged with the
increase of Pluronic F127 content in the casting solution [46].
Moreover, DMMSAPS was added to PSU before inducing
the phase separation of the solution. Micelles are then assumed
to be forming in the solution. Owing to the high polarity of the
solvent, the hydrophobic hydrocarbon chains are oriented to-
ward the interior of the micelle, leaving the hydrophilic groups
in direct contact with the solution. Throughout the phase sepa-
ration, these micelles act as a pore former. SEM images pre-
sented in Fig. 10 display the images of untreated and modified
PSU membranes. When DMMSAPS concentration is greater
than 0.5 wt %, DMMSAPS behaved similarly as a pore former
[45]. As the additive concentration increased, both surface and
cross sections revealed its important effects on porous struc-
ture. Larger pores were found on the surfaces and larger
cellules were located within the bulk. Therefore, when the
DMMSAPS concentration is greater than 0.5 wt %, the mem-
brane showed higher surface porosity.
3.2.3 Novel Morphology Control Techniques
Nonsolvent-induced phase separation (NIPS) is the most
widely used method to prepare PSU membranes for separation
processes. An advantage of NIPS is that it can be easily modi-
fied to prepare hollow-fiber membranes, which have high
membrane packing density. In the hollow-fiber spinning pro-
ChemBioEng Rev 2015, 2, No. 1, 22–43 27

Figure 10. SEM images of the surface and cross sections of the PSU membrane
at different DMMSAPS concentration [45].
cess, polymer solution (dope) is extruded through the annular
region of a spinneret, while bore fluid (a nonsolvent) is forced
through the inner capillary of the spinneret so as to form the
inner bore of fibers. The polymer solution is extruded into a
coagulation (nonsolvent) bath for NIPS to occur, forming po-
rous structures in the fiber walls. NIPS is widely used not only
to prepare polymer hollow fibers, but also to create inorganic
and organic-inorganic hybrid hollow-fiber membranes. Three
novel morphology control techniques for PSU membrane
based on NIPS are discussed below: phase separation micro-
molding, the so-called breath figure method, and a method
combining NIPS and self-assembly of block copolymers [47].
3.2.3.1 Phase Separation Micromolding
Several studies show that phase separation micromolding is a
newly developed method to prepare membranes with patterned
surfaces [48–50]. The PSU membranes with patterned struc-
ture can have a lot of potential applications in microfluidic de-
vices, scaffolds for tissue engineering, microsieves, and porous
molds for micro contact printing [51]. In this method, the
polymer solution is cast on a substrate with a designed pattern,
usually a silicon wafer with patterned structure fabricated using
photolithography. Phase separation of the polymer solution is
then induced either by immersing the solution with substrate
in a nonsolvent bath (the wet method), or by exposing it to
humid air (VIPS). The obtained porous PSU membranes have
a surface pattern that is a negative replica of the substrate. The
method could also be used to prepare a surface with two-tier
hierarchical structures that feature a super-hydrophobic prop-
erty [52]. Recent research studies have focused on using a poly
(dimethylsiloxane) (PDMS) replica mold as the substrate in-
stead of the silicon wafer, and on using VIPS to precipitate the
polymer solution instead of the wet method. In addition, it has
been shown that the PSU membranes with patterned surfaces
prepared by this method can effectively reduce the deposition
of microbial cells on them [53].
3.2.3.2 The Honeycomb Porous Structure of the Breath
Figure Method
The membranes prepared by the breath figure method have a
honeycomb structure, a two-dimensional array of hexagonal
pores, and were fabricated by water droplet condensation
accompanied with the fast solvent evaporation in humid air
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[54–57]. The breath figure method has been widely
used to prepare polymer films with honeycomb
surface structure [58]. A schematic diagram is giv-
en in Fig. 11 to illustrate this process [47]. The sol-
vent used in this method needs to be volatile and
immiscible with water. The evaporation of solvent
cooled down the surface, inducing condensation of
water vapor on the surface. Owing to the fact that
the solvent is immiscible with water, the phase sep-
aration occurred on the surface and formed the nu-
clei of water droplets that grew into hexagonal
pores. This method is usually called the breath fig-
ure method and can be categorized as a VIPS pro-
cess. However, this method was seldom used to
prepare porous membranes because the hexagonal
pores were not through-pores across the films. Recent re-
searches shed some light on how to resolve this problem. They
suggest that this issue can be fixed by casting a very thin film of
polymer solution, after which the membrane is transferred on-
to a porous substrate to form a thin selective layer for microfil-
tration [59, 60]. The resulting selected layer was highly porous
and the pore size was uniform throughout the membrane sur-
face.
a)
b)
c)
Figure 11. Schematic presentation of the breath figure method.
(a) Water vapor condenses on the surface of the polymer solution
because of the surface cooling caused by solvent evaporation.
(b) Water droplets form after the condensation. (c) Porous surface
forms after the polymer precipitation and water removal [47].
3.2.3.3 Combination of NIPS and Self-Assembly of Block
Copolymers
One of the challenges in membrane preparation is the need to
prepare membranes with uniform pore size, which offer high
membrane selectivity for mixtures with different particle (mo-
lecular) sizes [61]. The self-assembling nature of block copoly-
mers is an emerging technique used to form ordered structures
in nanometer scale within the range of 10–100 nm [62–64]. In
this process, a dense microphase segregated block-copolymer
ChemBioEng Rev 2015, 2, No. 1, 22–43 28
template is formed first, and then an etching or selective disso- 3.3.1 Effects of Polymer Concentration
lution process is applied to remove one of the blocks and form
uniform pores [62]. Another interesting technique has been de- At a PSU concentration of 15 wt % the final membranes had a
veloped recently to form nanoporous membranes with uniform pore size larger than 1 mm. To obtain membranes with smaller
pore size [65, 66]. This technique is called the self assembly and pore size, higher PSU concentrations of 16.5 wt %, 18 wt %, and
nonsolvent-induced phase separation. In this case, block co- 20 wt % were used while maintaining the PVP/PSU ratio at 1:1.
polymers are dissolved in carefully selected solvent mixtures in Fig. 12 shows the SEM photos of the PSU top surfaces at var-
order to allow the formation and assembly of copolymer mi- ious concentrations. With the increase of the PSU concentra-
celles in the solution. In the next step, the properly ordered tion from 15 wt % to 18 wt %, the number, size, and depth of
morphology of the copolymer micelles is then stabilized and concave defects in the PSU top surface gradually declined. At
frozen in the dry/wet phase separation method. This leads to 20 wt %, the surface observed was almost smooth. It must be
the creation of mesoporous membranes with very high pore emphasized that the higher viscosities are a direct outcome of
density and uniformity. During this process a number of essen- the relatively high polymer concentrations in the spinning
tial strategies of membrane manufacturing were identified. In solutions. Polymer chain dynamics and the thermodynamics/
particular, the solvent quality needs to be adjusted carefully kinetics of the system are two key factors in controlling the
when forming the needed self-assembly pattern [65]; the intro- membrane morphology, as will be discussed in the following
duction of metal ions to form metal-polymer complexation sections.
[68, 69], as well as the introduction of low-quality solvent for
the micelle coreblocks [69] have the potential to significantly
3.3.1.1 Chain Dynamics
stabilize the micelle structure in the solution; and lastly, the sol-
vent mixture needs to contain a volatile component that will
The PSU/PVPK90 blended solutions implemented in this ex-
promote a fast increase of polymer concentration and solution
periment can be viewed as an entangled polymer network swol-
viscosity before NIPS [69]. The self-assembly and nonsolvent-
len within the mixture of solvent and nonsolvent [78]. Notably,
induced phased separation method is a rather promising tech-
an increase of PSU and PVPK90 concentrations does contrib-
nique that will allow to prepare highly uniform nanoporous
ute to further entanglement of polymer chains. According to
PSU membranes on the commercial scale.
the findings of De Gennes, in the process of concentrating the
polymer solution the movement of a single polymer chain is
very much like a worm repetition process [79]. In theory, the
3.3 Sacrificial-Layer Approach polymer chains are made of a number of consecutively linked
segments. In these segments the polymer chains primarily in-
Although there are numerous preparation methods for PSU teract with themselves rather than other chains. As a conse-
microfiltration membranes [70–73], it is not easy to control the quence, the movement of the polymer chain is quite con-
morphology of the membrane. A new co-casting technique has strained, since the chain is only able to escape itself along the
been reported that would allow to control the morphology of axis. In other words, the concentrated solution containing en-
PSU based on different parameters [74, 75]. In a co-casting tangled chains reacts to external impact differently compared
process, a coating solution is simultaneously extruded with a to a low viscosity solution. When examined on a shorter time
support solution. During the immersion precipitation, the coat- scale, whenever there is an external impact, the entangled solu-
ing layer (sacrificial layer) delaminates from the
support layer (the membrane) [76]. After the co-
casting of PAN/DMF onto CA/DMF solutions, the a) b)
findings suggest that the delaminated coating layer
results in an open surface in the support layer [75].
Moreover, the co-casting of polyetherimide (PEI)/
N-methyl pyrrolidinone (NMP) onto PSU/polyvi-
nylpyrrolindone PVPK90/NMP solution leads to a
microfiltration (MF) PSU membrane with an open
surface, as has been reported earlier [74] and will c) d)
be discussed in the following sections.
In this study, the main parameters in controlling
the PSU membrane morphology via a co-casting
sacrificial approach were investigated. PEI/NMP
and PSU/PVPK90/NMP were used as the coating
and supporting solutions, respectively [77]. The
PSU concentration, additive concentration, coating Figure 12. Top surfaces of PSU membranes at different PSU concentrations. The
thickness, and coagulation bath temperature were PSU/PVPK90 concentration in weight percentage were: (a) 15/15; (b) 16.5/16.5;
the main factors affecting membrane morphology. (c) 18/18; (d) 20/20. The coating solution: PEI/NMP 17/83 wt %, the support solu-
tion: PSU/PVPK90/NMP, coagulation bath: water, temperature: 22 C [77].

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tion behaves like an elastic solid because the polymer chains do
not deform permanently [77]. As a result, the resistance to ex-
ternal impact of the PSU layer is growing with the increase in
PSU concentration. At high PSU concentrations the less con-
cave defects are located on the top surface [77].
3.3.1.2 Thermodynamics and Kinetics
In terms of thermodynamics, the highly concentrated polymer
solution is much closer to the binodal phase separation point
[78]. Thus, at the moment when the precipitation mixture is
reaching the interface between the PEI/PSU solutions, the pre-
cipitation of the highest concentrated PSU solution is notice-
ably quicker. Therefore, the surface becomes rigid at an earlier
stage, which implies that it can tolerate stronger external im-
pacts. For this reason, an increase of PSU concentration effec-
tively suppresses the formation of concave defects [77].
3.3.2 Effects of PVP Concentration
The influence of the PVP concentration on PSU membrane
properties was investigated by keeping a constant PSU concen-
tration at 20 wt % [77]. Fig. 13 shows the top surface and a
cross-section of PSU membranes. As illustrated in Fig. 13, the
cross-section of PSU membranes changed from finger-like
macrovoids structures to a macrovoids-free porous structure
with an increase of PVP concentration [77]. At 6 wt % PVP
concentration, the top surface revealed holes as large as 60 mm.
At 10 wt % PVP concentration, there were more holes with the
size of 20–30 mm, while a further increase of PVP concentra-
tion to 15 wt % indicated only a few shallow concave defects
and the top surface appeared quite open. Once the PVP con-
centration was up to 20 wt %, the concave defects disappeared
and a rather compact surface was observed. Due to the high
molecular weight of PVP, the PSU solution viscosity increased
exponentially as the PVP concentration increased. The increase
of polymer solution viscosity was ascribed to the entanglement
Figure 13. Effect of PVP content on the morphology of PSU membranes. PSU concentration was 20 wt %. The values in the photos are
the PSU/PVPK90 concentration in weight percentage. The coating solution: PEI/NMP 17/83 wt %, coagulation bath: water, temperature:
22 C [77].
www.ChemBioEngRev.de ª 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
of PSU and PVP chains. The entanglement of polymer chains
led to an elastic solid-like property as part of the response to
external impact, effectually suppressing the impact of finger-
like macrovoids in the PEI layer [77]. Owing to this, the con-
cave structure becomes less significant at higher PVP concen-
tration. As the PVP concentration decreased, both surface and
cross sections revealed the importance of their effects on po-
rous structure, as shown in Fig. 13. At a PSU and PVPK90 con-
centration of 20 and 6 wt %, respectively, the PSU exhibited a
large pore size and higher porosity. On the other hand, at a
PSU and PVPK90 concentration of 20 wt % (each), PSU
showed the smaller pore size and lowest porosity levels.
3.3.3 Effect of PEI Thickness
Illustrated in Fig. 14 are the SEM images of the top and bottom
surface of PSU membranes that were prepared at a PEI layer
thickness of 50 mm, 100 mm, and 450 mm, respectively [77]. Im-
ages indicate that as the PEI layer thickness increased, the PSU
membranes had larger pores and the concave defects noticeably
increased. However, as the PEI layer thickness increased, the
number of concave defects decreased. Once the macrovoids
penetrate deeper into the PEI solution where the cross-section
of the fingers is more extensive, they end up leaving larger in-
dented defects in the PSU surface. Alternatively, thicker layers
permit less macrovoids to grow deep enough per unit area be-
cause of the thickness effect, which results in fewer defects [78].
3.3.4 Effects of the Coagulant Temperature
During the immersion phase separation, the coagulation bath
temperature influences the diffusion rate of both solvent and
water that in turn influence membrane structure and perform-
ance [78]. It was found that at a water bath temperature above
70 C, PEI adhered well to PSU. Therefore, different water bath
temperatures below 70 C were investigated, specifically 22 C,
ChemBioEng Rev 2015, 2, No. 1, 22–43 30
 a)

b)

c)

Figure 14. Effect of PEI thickness on the PSU membrane top

and bottom surfaces. The coating solution: PEI/NMP 17/83 wt %,
bottom solution: PSU/PVP/NMP 15/15/70 wt %, coagulation:
water, temperature: 22 C. Top: top surface; bottom: bottom sur-
face [77].

45 C, and 65 C. The SEM photos of PSU membrane surfaces Figure 15. Effect of the coagulation bath temperature on the
are shown in Fig. 15 [77]. At 22 C, the membrane surface dem- PSU membrane top surfaces. The coating solution: PEI/NMP 17/
onstrated more macrovoids growing deep enough per unit area. 83 wt %, bottom solution: PSU/PVP/NMP 15/15/70 wt %, coagu-
lation: water. The coagulation bath temperatures were at
(a) 22 C; (b) 45 C; (c) 65 C [77].
3.4 Polysulfone Membranes Impregnated with
Nanoparticles a)
Syntheses of new polymeric PSU-nanotube composite mem-
branes using different types of nanotubes were reported in sev-
eral key research studies to investigate their effects on the mor-
phology of the membranes. In this section, different types of
nanotubes impregnated with PSU membranes are reviewed,
including carbon nanotubes, multiwalled carbon nanotubes,
silica nanoparticles, silver nanoparticles, titanium oxide nano- b)
particles, and zeolites.

3.4.1 Carbon Nanotube/Polysulfone Composite

Membranes

Carbon nanotube/polysulfone composite membranes were syn-

thesized to find ways of controlling morphology and enhancing
the performance using single-wall (SWNT) and double-wall
(DWNT) nanotubes [80]. As shown in Fig. 16, PSU mem-
branes with double-wall carbon nanotubes showed the pres-
ence of larger size pores in comparison with the untreated
PSU. The larger size of pores and relatively smaller compact
Figure 16. SEM images of PSU membranes; (a) untreated PSU;
(b) PSU with double-wall carbon nanotubes [80].
structure implies the applicability of the composite membrane
in the process of filtration of blood and other physiological liq-
uids (Pb and Hg), due to the advantages to the higher flow. The

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maximum adsorption capacity of untreated PSU was
0.3 mgPb2þ dm2 of membrane. Once the concentration of
SWNT was increased to 1 %, 3 %, and 5 %, the adsorption
capacity of PSU became 9.1, 29.9, and 49.8 mgPb2þ dm2 of
membrane, respectively. Alternatively, when the concentration
of DWNT was increased to 1 %, 3 %, and 5 %, respectively [80],
the adsorption capacity of PSU became 12.3, 35.4, and
56.2 mgPb2þ dm2 of membrane, respectively.
3.4.2 Multi-walled Carbon Nanotube/Polysulfone
Composite Membranes
Various research studies on polysulfone/carbon nanotubes
(CNT) composite membranes were conducted in order to find
ways of controlling morphology and enhancing their perform-
ance [81, 82]. Research indicates that polysulfone-blended
membranes show a porous morphology that can result in high
performance. The addition of MWNTs can help to reduce the
pore size, due to nano size (110–117 nm) diameters of MWNTs,
as shown in Fig. 17 [83]. The functionalization of the surface of
nanotubes elucidates the required physical bonds between the
polysulfone and the incorporated nanotube, which can influence
the formation of the porous structure. The decrease in pore size
of the membranes combined with a gradual increase in the
amount of carbon nanotubes is not particularly significant, as
the arrangement of carbon nanotubes in the membranes is less
manageable and controlled. The increase in carbon nanotube
makes the surface of the membrane more smooth (Fig. 17 b and
17 c) as the exchange process becomes slower, owing to the in-
a)
b)
c)
Figure 17. FESEM images of CNT/PSU composite membranes;
(a) 0.0 %, (b) 0.1 %, and (c) 1.0 % functionalized MWNTs [83].
www.ChemBioEngRev.de ª 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
crease in the viscosity of the blended solution [83]. The largest
visible pore size of the unblended polysulfone membrane
(Fig. 17 a) at lower magnification, while in the blended mem-
brane containing 1 % nanotubes, is less than 1 mm [83]. The in-
creased amount is also reflected by the membrane pore form,
size and contact angle measurements. When MWNT content is
very high (above 1 %), the density of MWNTs in the membrane
is high enough, and the steric hindrance and electrostatic inter-
actions between modified MWNTs and polysulfone, or modified
MWNTs and themselves can cause a portion of MWNTs to
irregularly aggregate in the membrane during the phase-inver-
sion, making the casting process difficult. For this reason, com-
posite mixtures containing MWNT above 1 % were not studied.
The high density of MWNTs in the membrane has the potential
to reduce porosity. The addition of MWNTs causes an increase
in hydrophilicity of the membrane (reduced contact angle) and
decrease in pore size, as shown in Tab. 1 [83]. These results can
be explained by the fact that during the phase inversion process
the hydrophilic MWNTs migrate spontaneously to the mem-
brane/liquid interface in order to reduce interfacial energy [82].
As the amount of MWNTs increases from 0.1–1.0 wt %, the PSU
hydrophobic membrane behaves more and more hydrophilic.
With the increase in MWNTs, there is a rise in the viscosity of
the blend solution. The solvent/nonsolvent exchange process
becomes slower, resulting in a smoother surface, while smaller
pore sizes through the pore size variations are not extending the
same influence in addition to the higher percentage of MWNTs.
Table 1. Variations of the pore size with the amount of amide-
functionalized CNTs [83].
MWNT [%] Pore size [mm] Contact angle q []
0.0 0.1079 77.7
0.1 0.028 77.6
0.2 0.026 77.6
0.5 0.025 77.5
0.7 0.025 76.3
1.0 0.025 26.7
Simultaneously improving both the permeability and selec-
tivity of porous membranes is one of the most challenging is-
sues in membrane research [84, 85]. Carbon nanotube mem-
branes were developed to achieve extremely high water flow
rate with sub-2-nm pore size, possibly attributed to the forma-
tion of so-called water wires in the confined space or friction-
less surface of nanotubes [86]. A new protein membrane was
also designed to obtain a flux as high as 9000 L m–2h–1bar–1 and
a pore size of less than 2.2 nm [87].
3.4.3 Silica Nanoparticles
Mixed-matrix membranes (MMMs) are based on PSU mem-
branes filled with inorganic particles as a way of improving
their gas separation performance. In a previously conducted
ChemBioEng Rev 2015, 2, No. 1, 22–43 32
study, MMMs were prepared from PSU containing embedded
nonporous 13-nm-sized fumed silica nanoparticles. The origi-
nal state of the silica nanoparticles was dispersed, but appeared
to form agglomerates in the polymer matrix and allowed for
the cluster size increases at higher silica content of 20 % [88].
The untreated PSU showed the average diameter of free vol-
ume of 0.42 nm, while the agglomerate size of silica nanoparti-
cles was as high as 100 nm. However, it was impossible to de-
tect the molecular interface between the polymer and silica
network at which the presence of voids can be properly consid-
ered [89]. Such behavior can result from an increase in free vol-
ume due to the inefficient chain packing as well as the presence
of extra void volume at the interface level between polymer
and silica clusters [88–90].
3.4.4 Silver Nanoparticles
Silver nanoparticles incorporated into the PSU ultrafiltration
membranes exhibited antimicrobial properties towards a varie-
ty of bacteria. A 0.9 % silver nanoparticle incorporation in-
creased the membrane hydrophilicity by 10 % and significantly
reduced the potential of PSU membranes toward the fouling
phenomenon. However, this study effectually proved that the
PSU in both cases showed highly similar morphologies, as they
showcased the same surface porosity and pore size distribution
[91]. Another study [92] indicated the effects of casting mix-
ture composition and silver nanoparticle incorporation route
on the morphological properties of prepared PSU membranes.
Silver nanoparticles were either synthesized ex situ and then
added to the casting solution as an organ sol, or produced in
the casting solution via in situ reduction of ionic silver by the
polymer solvent. Larger nanoparticles were mostly located in
the skin layer of composites prepared via the ex situ method,
while in situ reduction of silver led to the formation of smaller
nanoparticles homogeneously distributed along the membrane
cross-section. In some cases, the incorporation of silver nano-
particles formed from the ex situ method resulted in a macro-
void widening. The surface of the silver-free PSU membranes
featured low porosity with pore sizes of less than 10 nm. The
composite membranes prepared via the in situ method showed
a significantly more porous skin, with interconnected surface
pores of 30–100 nm in size, while the composite membranes
prepared via the ex situ method membranes had well defined
larger pores with the typical pore size of 0.5 mm.
3.4.5 TiO2 Nanoparticles
Table 2. The effect of titanious oxide nanoparticles and the air gap on the morphological char-
acteristics of PSU [94].
A number of studies have been
conducted in an attempt to in-
Membrane TiO2 Content [%]
crease the surface porosity of the
polysulfone membrane surface PSF 0 0
through the addition of metal
PSF–T0 2 0
nanoparticles to the polymer ma-
trix in order to reduce the fouling PSF–T5 2 5
potential and improve the mem- PSF–T13 2 13
brane performance. TiO2 nanopar-
www.ChemBioEngRev.de ª 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ticles have proven to be successful in mitigating fouling of
organic matter onto PSU [93]. The TiO2 nanoparticles nano-
composite membrane featured an asymmetric membrane con-
sisting of a compact layer and a porous layer. The thickness of
skin layer increased with the TiO2 nanoparticles concentration.
The addition of TiO2 nanoparticles filler resulted in an increase
of pore numbers in the porous skin layer, compared with the
PSU membrane, hence, resulting in an increase in the permeate
flux. As indicated in Tab. 2, the titanium oxide nanoparticles
content and the air gap affected the morphology characteristics
of PSU membrane, such as the MWCO, inner diameter, and
outer diameter of pores. As the titanium oxide nanoparticles
content was increased to 2 % and the air gap reached 13 cm,
the MWCO increased from 57 to 90 kDa. Furthermore, the
metal oxide nanoparticles enhanced the surface hydrophilicty
and the antifouling properties of PSU membrane [93, 94].
3.4.6 Zeolite Incorporation
Although these new membranes are still far from an effective
industrial application, they have inspired new trends in re-
search exploration of diverse methods for modifying conven-
tional polymeric membranes with high permeability, selectivity,
and hydrophilicity. The atomic layer deposition of TiO2 on
polyvinylidene difluoride (PVDF) membranes has been proven
to simultaneously acquire enhanced permeability and selectiv-
ity [95]. However, most of the pre-existing work on modifying
PSU membranes with improved hydrophilicity and fouling re-
sistance had eventually sacrificed the extent of selectivity or
permeability.
Zeolites are microporous crystalline materials and are usu-
ally used as catalysts, ion-exchangers, and absorbents because
of their cage-like structure, superior hydrophilicity, precise
nanochannel, negative charges, and other advantageous charac-
teristics. NaA zeolite particles are generally stable within a
range of aqueous and organic solvents, and as such cannot be
washed out rapidly from the hybrid membranes [96]. Zeolites
have been widely used for the preparation of mixed matrix
membranes for gas separation due to their precise separation
and size exclusion [97–100]. One research publication reported
on the influence of zeolite incorporation in membrane synthe-
sis on membrane morphology and performance. The PSU
membrane was fabricated by the classical phase inversion
method [101]. Measured amounts of PSU, polyethylene glycol
PEG-600, and zeolite were sequentially dissolved in N,N-di-
Air gap [cm] MWCO [kDa] ID [mm] OD [mm]
57 0.493 +0.001 0.978 +0.011
61 0.517 +0.006 0.993 +0.003
77 0.506 +0.003 0.947 +0.001
90 0.481 +0.001 0.908 +0.007
ChemBioEng Rev 2015, 2, No. 1, 22–43 33
methylacetamide (DMAc) solution. More details Table 3. Compositions of the casting solutions for PSU membranes [102]. a) Ze-
about the procedures of this process were reported olite 4A dosage was based on 100 g of Pa-3 casting solution.
in [102]. The compositions of the casting solutions
for the membranes are summarized in Tab. 3. Membranes PEG-600 Zeolite 4A [g]a) PSU [wt %] DMAc [wt %]
The morphology of the membrane at different Pa-1 0 0.0 20 80
compositions was observed. When the PEG-600
dosage was increased from 0 to 6 and 8 %, both the Pa-2 6 0.0 20 74
pore numbers and pore size for Pa-1, Pa-2, and Pa-3 8 0.0 20 72
Pa-3, increased slightly. This was due to the fact
that a higher content of PEG-600 can much more Pb-1 8 0.3 20 72
easily diffuse into a coagulation bath, because of its Pb-2 8 1.5 20 72
strong interaction with water as a porogen, which
Pb-3 8 3.0 20 72
causes the formation of additional surface pores
and finger-like pores in the cross section. By em-
bedding zeolite 4A into the PSU membrane, the
top surface of Pb-1, Pb-2 and Pb-3 was made rougher and still is a slight aggregation of zeolite particles, especially in the
denser with more nodule-like structures if compared to Pa-1, Pb-3 case with high content of zeolite, as shown in Fig. 18.
Pa-2 and Pa-3. This resulted in a noticeably smaller pore size. In another study, PSU-based nanocomposite membranes
Due to the high surface area ratio, the adsorption property, and were prepared using zeolite nanoparticles as additive, and
hydrogen bonding interaction of zeolites, there are strong in- D-a-tocopheryl polyethylene glycol succinate (TPGS) as a
teractions between zeolite 4A and PSU casting solution. These compatibilizer [103]. Various additive concentrations were
interactions resulted in a denser and selective skin layers by used to investigate its effects on membrane morphology, prop-
increasing the viscosity of the PSU/DMAc/PEG solutions, erties, and performance. Based on these, a microstructural
slowing down the phase inversion process and delaying the de- model was proposed to explain the effects of additives on mem-
mixing. Magnified images of Pb-1, Pb-2, and Pb-3 in Fig. 18 re- brane pore characteristics. Since both are highly miscible, the
vealed that zeolites 4A with the mean particle size of 0.5 mm solvent (NMP) and nonsolvent (water) molecules diffuse dur-
were embedded in both, the selective layer with the thickness ing the hollow-fiber membrane (HFM) formation by phase
around 2 mm, and on the wall of finger-like pores [102]. This inversion of a polymer solution of PSU (MW = 79 000). In par-
indicates that the fast flow paths were formed in both, the nano ticular, this occurs on the inner side of the membranes where
channel and free volume between zeolites and the polymer the membrane skin is formed. To modulate skin microstruc-
matrix. Furthermore, no obvious zeolite agglomerates were ture, the zeolite nanoparticles (40–60 nm) are suspended in
observed in fingers or surfaces in case of Pb-1. However, there PSU/NMP solution as additives, however, their hydrophilic

Figure 18. Cross-sections SEM images of Pa-1, Pa-2, Pa-3, Pb-1, Pb-2, and Pb-3 [102].

www.ChemBioEngRev.de ª 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ChemBioEng Rev 2015, 2, No. 1, 22–43 34
nature renders them incompatible with the hydrophobic PSU.
This, in turn, leads to the undesirable formation of zeolite ag-
gregates in the polymer matrix [104]. In order to overcome
this, TPGS (MW = 1513) is implemented as a compatibilizer
because it includes both hydrophilic (PEG) and hydrophobic
(tocopheryl) groups [105]. Notably, zeolite features a micro-
porous crystalline structure which helps to increase the inter-
action with polysulfone/TPGS in the dope solution. Such a
quick solvent/nonsolvent diffusion process across the PSU sol-
ution film produces an incompatible environment for PSU
macromolecules. In an attempt to decrease this unfavorable in-
teraction, the PSU macromolecules actively cluster around zeo-
lite nanoparticles. Due to shared PSU chains, these clusters are
interconnected together by entanglement. These clusters are
also called nodules and are illustrated in the microstructural
models in Fig. 19. The sizes of pores in these composite mem-
branes correspond to the interstices between nodules. It was
determined that the pore size and pore number are the defining
characteristics that determine the flux and molecular weight
cutoff (MWCO) of a HFM, since it can be shaped by the prop-
erties of the suspension of zeolite additive. In the case of a uni-
form suspension, illustrated in Fig. 19 a, a large number of
small and uniformly-sized pores are formed. Alternatively, in
the case of the zeolite aggregates, illustrated in Fig. 19 b, a num-
a)
b)
Figure 19. A proposed microstructural model: (a) Uniform sized and nanoscale disper-
sion of zeolite nanoparticles in dope solution lead to small size nodules formation and
result in small pore size with high pore density; (b) an agglomerate of zeolite nanoparti-
cles in dope solution lead to large size nodules formation and result in large pore size
with reduced pore density [103].
www.ChemBioEngRev.de ª 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ber of large-sized nodules and a small number of large-sized
pores are formed.
3.5 Surfactants
The addition of hydrophilic surfactant into the PSU polymeric
membrane had a significant effect on the morphological charac-
teristics of the PSU, due to the increase of surface porosity. The
addition of Tetronic 1107 hydrophilic surfactants (ethylenedi-
amine tetrakis(ethoxylated-block-propoxylate) tetrol) into the
casting solution resulted in a PSU with high porosity/bigger
pores on the top surface and, as a consequence, a higher pure
water flux. At the Tetronic 1107 concentration of 0, 2, 4, and
6 %, the mean pore size of PSU was 7, 9, 11.5, and 13 nm, respec-
tively [106]. Another study used Tween 20 (polyoxyethylene
sorbitan monolaurate) as a hydrophilic surfactant in the casting
solution of PSU preparation. The addition of 4 % of Tween 20
resulted in an increase in the surface porosity by 7 % [107].
Also, the free volume in the skin of PSU hollow fibers can be
increased by adding the Lewis-acid nonsolvent in the casting
solution containing the Lewis-base solvent [108, 109]. Further-
more, the addition of surfactants in the casting solution can in-
fluence the macrovoids formation. For a hydrophilic coagulant,
e.g., water, hydrophilic surfactants can en-
hance the formation of macrovoids, while
lipophilic surfactants can suppress the for-
mation of macrovoids. The size of macro-
voids decreases as the surfactant content in-
creases from 15 to 40 %, causing a decrease
in the permeation rate while the separation
factor increases.
4 Effect of Morphology
Control on Mechanical
Properties and Chemical
Stability
Although PSU membranes exhibit thermal
stability and comprehensive strength prop-
erties, they consist of a tough polymer be-
cause of their high glass-transition temper-
ature [27]. Moreover, PSU membranes are
not proficient in terms of mechanical prop-
erties with bulky structure, and their bind-
ing force between fibers is low. Enhancing
the flexibility of membrane fibers and de-
creasing its diameter were achieved by con-
trolling the PSU morphology by heat treat-
ment. After the process of tension heating
at 190 C for three hours, dimensional sta-
bility, integrity, appearance, and mechani-
cal properties were improved. In addition,
the chemical stability of the alcohol solu-
tion also noticeably increased while the
membrane rapidly shrunk in the acetone
solution [23].
ChemBioEng Rev 2015, 2, No. 1, 22–43 35
 The structure of the PSU membrane did not reach the stable properties of single fiber, eventually yielding the drop of the
state and was observed to be a bulky structure, even though it PSU membrane mechanical properties. Thus, the best mechan-
was already formed, as illustrated by Fig. 20 a [23]. During the ical properties of the PSU membrane were attained by treating
heating process, the enhancing energy of some bound water the membrane with tension heating at 190 C for three hours.
and adsorption water molecules in the membrane enabled The chemical stability of a tension-heated membrane was
themselves to escape by overcoming the binding of hydrogen better than that of an untreated membrane, and it was the heat
bonding and other molecular interaction. At the same time, the treatment that improved the appearance and dimensional
movement of macromolecular chains was enhanced while their stability of PSU membrane [23, 110]. Moreover, the alcohol
activation energy increased [110]. Although this promoted the solution could be used to rinse the tension-heated PSU mem-
mutual attraction of polar groups within and among the molec- brane during practical applications. It became apparent that
ular chains, it also reduced the space in the membranes. The the heat treatment significantly influenced the morphology of
mechanical properties of the membrane were enhanced by the the membrane which in turn promoted the chemical stability
fact that the membrane fibers tend to be curved. Fig. 20 b shows of PSU membrane, as presented in Fig. 21 [23].
that after the heat treatment, the membrane surface became
significantly smoother, while the fiber arrangements became a)
closer. During the period of relaxation, the internal forces were
absent, resulting in the disentanglement and enhancement of
the connecting points [23]. This was further accompanied by a
formation of some new connections. For this reason, a much
more advantageous arrangement of the fiber molecules, im-
provement of the mechanical properties, and enhancement of
structural stability were facilitated.
On the other hand, when undergoing tension heating the
molecular movement was amplified. Both the heat and the ten-
sion enabled molecules with folding chains to unfold, and then
rearrange along the direction of the external force [110]. As a
consequence, the orientation degree of fibers in amorphous re-
gions and density enlarged, causing the initial modules of b)
breaking stress and breaking strain to increase. The heat also
helped degrading weak bonds in fiber macromolecules. In ad-
dition, the raise in temperature led to a reduction in the inter-
actions between molecules, causing mechanical properties to
deteriorate. This explains why some PSU molecular chains be-
gan to break down and the mechanical properties decreased
when the temperature exceeded 190 C [23]. One hour heat
treatment caused the initial modulus, breaking stress, and
breaking strain to noticeably increase. In the case where the
heating time lasted for three hours, the initial modulus and
breaking stress were slightly enlarged, while the change in
breaking strain was not immediately apparent. When the heat-
ing time reached five hours, the initial modulus, breaking
stress, and breaking strain all began to rapidly decline. As part Figure 21. (a) Photos of as-spun membranes immersed in sol-
vents for 8 d. (b) Photos of tension-heated membranes (190 C,
of the tension heating process, the mechanical properties im-
3 h) immersed in solvents for 8 d [23].
proved if treated within a specific period of heating time, while
the effect of extended heating time became equivalent to raising
the temperature [27]. When the heating time reached five Controlling the PSU membrane morphology by inserting
hours, the overly-extensive heating time caused the degrada- nanotubes was found to be an effective way to increase the
tion of some molecular chains and the decline of mechanical thermal stability of polysulfone, and ensuring that the thermal
degradation occurs at comparatively high tempera-
tures [83]. Furthermore, the impregnated nano-
a) b) tubes resulted in a higher hydrophilicity, reduced
contact angle, greater adsorptive nature, and a re-
duced pore size in the range of 20–30 nm. These re-
sults can be explained by the fact that during the
phase inversion process the hydrophilic nanotubes
migrate spontaneously to the membrane/liquid in-
terface to reduce interfacial energy [82]. With the
Figure 20. Photos of the PSU membrane before and after tension heating treat- increase in nanotubes, there is a rise in the viscosity
ment [23]. of the blend solution. The solvent/nonsolvent ex-

www.ChemBioEngRev.de ª 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ChemBioEng Rev 2015, 2, No. 1, 22–43 36
change process becomes slower, resulting in smoother surface,
and smaller pore sizes.
The reduced pore sizes and high adsorptivity make mem-
branes effective in metal removal from drinking water. The re-
jection percentage of heavy metals was found to increase as the
amount of MWNTs [87] was raised. The glass transition tem-
perature (Tg) of PSU membranes noticeably decreased from
183 to 139 C in ternary systems, when PEG-600 dosage in-
creased from 0 to 8 % due to the more flexible conformation
re-arrangement of PSU macromolecule chains. Further addi-
tion of zeolite 4A slightly increased Tg from 138 to 149 C,
once the zeolite dosage increased from 0.3 to 3.0 g, by tighten-
ing up the polymer chains via hydrogen bonding and other in-
termolecular interactions [110]. The use of nonwoven enforce-
ment significantly improved the tensile strength of PSU
membranes if compared to the membranes with woven fabric
supports. The tensile strength, elongation at break, and peel
strength of Pa-2 and Pa-3 decreased slightly due to the addition
of PEG if compared to Pa-1 featuring more finger-like pores.
However, further addition of zeolite 4A increased peel strength,
while no immediate effect was seen for the elongation at break.
The tensile strength of the membrane appeared to first decrease
from Pa-3 to Pb-1, when 0.3 g of zeolite was added, and then to
increase from Pb-1 to Pb-3, when more zeolites was added. It
was determined that controlling the morphology of HFM could
be enhanced with the presence of air gaps, which in turn re-
sulted in an improvement of the PSU membrane thermal prop-
erties [43]. Moreover, PSU membranes from blended compo-
sitions featuring an enhanced membrane porosity and
hydrophilic properties demonstrated good chemical and ther-
mal stabilities [45, 47, 77]. Moreover the addition of 2 % tita-
nium oxide nanoparticles resulted in a significant improvement
of the tensile strength and hydrophilic property, even though
the membrane thickness was negatively affected [93].
5 Effect of Morphology Control on PSU
Membrane Performance
The actual performance of a membrane is determined by two
different factors, namely its permeability and selectivity. There-
fore, the effect of morphology control on membrane perform-
ance in wastewater treatment applications was investigated
based on the permeate flux and the rejection percentage of the
contaminants. It was reported that increasing the polymer con-
centration via casting sacrificial approach had a significant ef-
fect on the membrane morphology, causing the favorable per-
formance of the membrane [77]. At 15 wt %, the membrane
showed a maximum pore size of about 1.7 mm and a mean flow
pore size of 1.2 mm. When the PSU concentration is increased
to 20 wt %, the maximum and mean pore sizes were 0.50 mm
and 0.22 mm, respectively. As a consequence, when PSU con-
centration increased from 15 to 20 wt %, the water permeability
declined from 55 000 to 10 000 L m–2h–1bar–1. In a sacrificial
layer method for PSU membrane synthesis, using solutions
containing PVP lower than 6 wt %, no detectable permeability
was observed. When the PVP concentration was increased
from 6 wt % to 10 wt %, the water permeability reached the
maximum of 14 000 L m–2h–1bar–1. This contributed to the in-
www.ChemBioEngRev.de ª 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
creasing of the pore size to the maximum of 1.0 mm and to the
augmentation of porosity to 75 %. A further increase of PVP
concentration to 20 wt % caused the pore size to dramatically
decrease to 0.6 mm. The rapid decrease in pore size could be at-
tributed to the increase of the entanglement in polymer chains.
More entanglement in polymer chains corresponds to higher
polymer chain repetition time. During precipitation, the en-
tangled PSU/PVP chains act as a physical cross-linked chain
network, hindering the growth of the polymer-lean phase. As a
consequence, the membrane pores are not allowed to grow,
which causes small pores [77]. The small pore size at a high
PVP concentration compels the membrane to develop a higher
resistance to convective flow, thus lowering its permeability. In
this method, the porosity had slightly declined as the PEI thick-
ness increased. A thicker PEI coating allowed the polymer-lean
phases in PSU to have more time to grow into larger pores. On
the other hand, the time for water to diffuse into the sublayer
was extended, leading to more solvent out-diffusion from the
PSU solution. Owing to this, the total polymer solution volume
was smaller at a thicker PEI layer, causing the final membrane
to have lower porosity. Alternatively, increasing the thickness
from 50 to 450 mm resulted in an increase in pore size from 0.4
to 2 mm, which facilitated an increase in the permeability from
10 000 to 130 000 L m–2h–1bar–1. It was determined that at a
higher coagulation bath temperature in the sacrificial layer
method more open surface was obtained, and less concave de-
fects were observed [77]. The mean pore size increased from
1.25 to 2.2 mm when the bath temperature increased from 22 to
65 C. Owing to this, the water permeability showed a signifi-
cant increase from 55 000 to 152 000 L m–2h–1bar–1 [77]. Over-
all, the results suggest that PSU MF membrane morphology
and permeability in co-casting could be controlled by adjusting
PSU concentration, PVP concentration, PEI coating layer
thickness, and coagulation bath temperature.
Another study investigated the performance of hollow fiber
membranes enhanced with the zeolite incorporation [103]. In-
creasing the pore size resulted in an increase in MWCO as well as
an increase in membrane performance. The mechanical aspects
indicated that the addition of nanoparticles weakened the nano-
composite HFMs if compared to pure PSU HFMs, probably due
to the weak interaction caused by the passive nature of zeolite and
PSU. This study may be useful for the processes involved in tun-
ing membrane properties using nanoparticles [103].
PSU with CNTs membranes showed an improvement in both
porosity and hydrophilicity. Industrial waste water is a major
source of various kinds of metal pollution in natural water
[111, 112]. These heavy metal ions remain stable despite persistent
environmental contaminations, since they are neither degraded
nor destroyed. A wide variety of techniques for the removal of
heavy metals from water are available. These include ion ex-
change [113, 114], reverse osmosis, and nanofiltration [115]. The
presence of nanotubes effectively increases thermal stability of
polysulfone, while thermal degradation occurs at comparatively
high temperatures. These influences make the membranes more
hydrophilic, ensure greater adsorptive nature, and reduce pore
size to the range of 20–30 nm. The reduced pore sizes and high
adsorptivity help membranes to remain efficient during the metal
removal from drinking water. The rejection percentage of heavy
metal was found to increase with increasing amounts of MWNTs,
ChemBioEng Rev 2015, 2, No. 1, 22–43 37
as presented in Tab. 4. Pb-3 ultrafiltration membrane exhibited a
mean pore size of 21.7 nm, pure water flux of 500 L m–2h–1, 97.0 %
BSA rejection, and 88.6 % pepsin rejection. In summary, the
tradeoff between permeability and selectivity of PSU ultrafiltra-
tion membranes was surmounted by the embedding of zeolite
4A, due to its morphology regulation, enriched nanochannels,
and negative charges.
Table 4. Removal studies of metal ions at pH 2.6 for amide
functionalized MWNT/PSU at pressure of 0.49 MPa [83].
CNT [%] Removal capacity [%]
hibited antimicrobial properties towards a variety of bacteria
and reduced biofouling and virus penetration [91]. The addi-
tion of metal nanoparticle fillers into PSU membranes re-
sulted in the increase of the pore numbers in the porous skin
layer if compared with the pristine PSU membrane. The hy-
drophilicity was increased due to the enhancement of the
antifouling properties of the membrane, which in turn en-
hanced the membrane flux [93]. Tab. 5 indicates that the
contact angle was reduced with the addition of metal nano-
particle fillers for selected nanocomposites, which resulted in
a substantial increase in pure water permeability [94].

Cr (VI) Cu (II) Pb (II) Cd (II) As (III) Table 5. Effect of TiO2 content on the performance of the PSU
membrane [94].
0.1 80.4 85.6 72.0 72.8 71.3

0.2 89.6 88.2 77.6 74.9 75.3 Membrane TiO2 content [%] Air gap [cm] PWP [L m–2h–1]

0.5 90.7 90.6 87.8 77.4 77.9 PSU 0 0 59.20 + 0.64

0.7 92.8 90.9 88.2 77.9 79.2 PSU-T0 2 0 78.33 + 0.52

1.0 94.2 93.1 90.1 78.2 79.4 PSU-T5 2 5 92.83 + 0.09

0.0 10.2 10.1 10.5 9.9 10.9 PSU-T13 2 13 120.11 + 1.08

The addition of hydrophilic surfactants had a significant

Morphology control of PSU membranes, by increasing the
porosity and membrane pore size, resulted in a significantly
better membrane performance as demonstrated by the heat
treatment [23]. Moreover, it was found that by controlling the
morphology of hollow fiber membranes, by enhancing the
presence of air gaps, resulted in an enhancement of PSU mem-
brane performance. This enhancement was due to macrovoids
and finger-like intrusions that have a considerably influence on
fiber performance [43]. PSU membranes prepared by blending
an amphiphilic additive, Pluronic F127 or DMMSAPS, with
PSU prior to inducing the phase separation of solution demon-
strated higher performance than PSU prepared without the
additives [45].
The removal of Pb2+ and Hg2+ by dialysis from 10–5 M-sol-
utions using CNT/PSU composite membranes allowed for a
superior retention, especially in the case of the membranes
with double-wall carbon nanotubes [80]. The retention of
Pb2+ achieved was 93, 90, and 82 %, after an hour using un-
treated PSU, SWNT/PSU, and DWNT/PSU, respectively.
Therewhile the retention of Hg2+ achieved 97 %, 92 %, 71 %,
after an hour using untreated PSU, SWNT/PSU, and
DWNT/PSU, respectively [80]. The addition of silica nano-
particles to PSU membranes resulted in a significant increase
in free volume. As a consequence, the gas permeability of
PSU grew with increasing silica content, due to the ineffi-
cient chain packing, as well as the presence of extra void vol-
ume at the interface between polymer and silica clusters.
Moreover, the permeability of gases with larger molecules
was further enhanced by the addition of silica owing to the
increase in free volume. The increased free volume led to a
higher diffusion coefficient and permeability, resulting in a
reduction in pure gas selectivity [88]. PSU membrane im-
pregnated with silver nanoparticles caused an increase in the
pure water permeability from 408–532 L m–2h–1bar–1, and ex-
effect on the morphological characterization and hydrophilicity
of the PSU membranes [106–109]. The contact angle of PSU
membrane was decreased and the membrane performance was
improved as the content of Tetronic 1107 increased. The
contact angel was 73.6, 64.9, 58.1, and 55.8 when the Tetronic
1107 content was at 0, 2, 4, and 6 wt %, respectively. Further-
more, the pure water flux was 38.5, 55.3, 62.9, and 62.9 L m–2h–1
when the Tetronic 1107 content was at 0, 2, 4, 6 wt %, respec-
tively [104]. Finally, the pure water flux of PSU membranes
increased from 97 to 132 L m–2h–1 as the 6 wt % of Tween 20
hydrophilic surfactant concentration was added [107].
6 Effect of Morphology Control
on Membrane Fouling
In the filtration processes, membrane fouling is a determining
factor in membrane lifetime. Once the membrane is contami-
nated by organic, inorganic, or biological substances, backwash
cleaning has a limited effect on the recovery of the original per-
formance of the membrane. In addition, in the cases with a
long operation period, membrane fouling is not completely re-
versible by the back-washing. To regain the membrane perme-
ability, a chemical cleaning becomes necessary. Chemical clean-
ing reduces the membrane lifetime. Fouling leads to higher
operating costs, higher energy demand, reduced the membrane
lifetime, and increased the cleaning frequency. In a sea-water
desalination plant, the cost of the membrane unit is about
20–25 % of the total capital cost. Usually about 10 % of the
membrane is replaced annually so as to maintain the targeted
product quality and quantity [29]. The permeate flux and
transmembrane pressure (TMP) are the best indicators of
membrane fouling. Membrane fouling leads to a significant in-
crease in hydraulic resistance, manifested through a declined

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permeate flux or TMP increase, when the process is operated
under constant-TMP or constant-flux conditions, respectively.
In a system where the permeate flux is maintained by raising
TMP, the energy required to achieve filtration increases result-
ing in more power consumption. For a plant with a 100 m3 d–1
capacity, the energy consumption is more than 10 KWh m–3,
which can be reduced to 3.5 KWh m–3 if the fouling is under
control [29]. Notably, the membrane antifouling property has
been connected to membrane morphology. This finding is es-
sential for membrane filtration since an improvement in filtra-
tion capacity can facilitate less frequent chemical cleanings and
a lower operational cost. Thus, an MF membrane with a dis-
tinctly open surface morphology is desirable in a filtration pro-
cesses. Membrane pore size and membrane porosity govern the
membrane morphology by enhancing membrane performance
and reducing membrane fouling [26].
In the previously conducted study a mathematical model
was developed using a homogeneous membrane with a uni-
form pore size and nonuniform pore size membranes [29, 30]
for the ultrafiltration of latex paint solution with a wide range
of particle size distribution. The model indicated that the pore
size, surface porosity, pore length, density of membrane pores
per unit membrane surface area, and membrane tortuosity in-
fluence the mass of fouling attached to the membrane surface,
as well as contribute to the increase of transmembrane pressure
due to membrane fouling. The tortuosity of the membrane is
the ratio between the membrane thickness and the actual path
that the small particles flow through the membrane pore. As a
consequence, a higher tortuosity influences membrane pore
plugging and increases the potential of the attached particles to
the membrane pore walls. The size of the latex particles and
membrane pores were considered as the primary factor in de-
termining the amount of surface fouling, i.e., cake layer forma-
tion or pore blocking, and adsorptive internal plugging. The
pore size distribution had a significant effect on the mass of
fouling retained by the membrane and the increase in trans-
membrane pressure at the same operating conditions. The cel-
lulose acetate membrane with a MWCO of 20 000 had 0.01 mm
at 80 % of the pore size distribution, which resulted in the
smallest experimental values of the mass of fouling and in a rise
in transmembrane pressure. In case of ultrafilic and PVDF
membranes with MWCO of 100 000, an increase in pore size
resulted in a greater flow through the membrane pores and
more permeate flux. Hence, the chances for the particle-to-par-
ticle and particle-to-membrane collision and attachment
increased. As a consequence, both the mass of fouling and
transmembrane pressure increased while at same operating
conditions.
The polymeric PSU-nanotube composite membranes had a
noticeable effect on the surface porosity and the membrane
pore size. Consequently, surface porosity and membrane pore
size had a significant impact on reducing the PSU membrane
fouling phenomenon [80, 88–94]. The incorporation of 0.9 %
silver nanoparticles increased membrane hydrophilicity by
10 % and reduced the potential of the PSU membrane toward
the fouling phenomenon [91].
It has been reported that the protein fouling behavior of PSU
composite membranes by bovine serum albumin (BSA) has
been drastically reduced due to the presence of nanotubes [83].
www.ChemBioEngRev.de ª 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
The reason stems from the fact that the polysulfone membrane
impregnated with nanotubes was more hydrophilic. Moreover,
blending an amphiphilic additive before VIPS into the PSU
membrane influenced the morphology of the membrane, fur-
ther demonstrating antifouling properties and increasing sur-
face hydrophilicity. It was determined that adding Pluronic
F127 and DMMSAPS caused further resistance to protein ad-
sorption on the membrane surface and acted as anti-biofouling
for the polysulfone membrane [45]. For 5 wt % of Pluronic
F127 concentration, the adsorption was 18 % of the untreated
PSU membrane. For this reason, Pluronic F127 was proved to
function as an efficient anti-biofouling agent.
Furthermore, zeolite incorporation showed a significant
effect in reducing PSU membrane fouling by BSA solution.
Fig. 22 shows the permeate flux of PSU for filtering a
1000 mg L–1 BSA aqueous solution. All the membranes ex-
hibited a declined flux trend due to BSA fouling. Nevertheless,
the addition of zeolite 4A improved BSA permeate flux to some
extent [99]. Notably, zeolite 4A particles embedded in the
membrane are mainly responsible for the increased roughness.
The mean value of the surface roughness (Ra) increased from
28.6 nm up to 63.1 nm, 71.7 nm, and 103.0 nm, after the embed-
ding of 0.3, 1.5, and 3 g of zeolite to 100 g of the Pa-3 casting
solution, respectively. As a consequence, the deposition of BSA
on the membrane surface was reduced. In addition, zeolites 4A
with the mean particle size of 0.5 mm were embedded in both,
the selective layer with the thickness around 2 mm, and on the
wall of finger-like pores, as shown in Fig. 18 [102]. This indi-
cates that the fast flow paths were formed in both the nano
channel and free volume between zeolites and the polymer
matrix.
Figure 22. Permeate flux of PSU membranes for filtering
1000 mg L–1 BSA aqueous solution [102].
7 Outlook
Most of the research focused on the preparation of membranes
containing copolymers and the evaluation of their separation
performance. Further research is needed to clarify how copoly-
mers segregate during membrane formation, and how micro-
phase separation of copolymers interacts with NIPS. NIPS of
polymer solutions containing inorganic particles have attracted
attention from researchers, especially with regard to the prepa-
ration of organic–inorganic hybrid membranes or precursors
of inorganic membranes. In this area, more fundamental stud-
ChemBioEng Rev 2015, 2, No. 1, 22–43 39
ies are necessary so to elucidate the underlying mechanisms of
the effect of the phase separation process on the distribution of
particles in the membrane, and understand how inorganic
particles influence the structure of the prepared membranes
(precursors). Other studies have identified different techniques
that can be applied to alternative types of membranes rather
than PSU. Some of these studies investigated the effects of di-
luent on isotactic polypropylene membrane morphology and
the effects of adding different ethanol amines to nanoporous
polyethersulfone. The results indicate a degree of improvement
in the membrane surface porosity and performance. Moreover,
ozonation, plasma graft-filling polymerization, and UV irradia-
tion have been applied to PVDF membranes. The results of
these applications demonstrated higher surface hydrophilicity,
while PVDF demonstrated antifouling properties. Although
these techniques have a great practical potential, they are yet to
be tried with PSU membranes.
8 Summary
The key factor in the development and application of PSU
membranes is the control of its polymeric morphology, due to
the extent to which membrane morphology can influence
membrane performance. Membrane pore size and membrane
porosity tend to govern membrane morphology, which enhan-
ces membrane performance and reduces membrane fouling.
Increasing the pore size, surface porosity, and macrovoids re-
sult in an enhanced membrane performance. Several tech-
niques and strategies of controlling the morphology of PSU
membranes have been extensively examined, and the effect of
the morphological alteration of the membrane on its mechani-
cal properties, chemical stability, performance and fouling has
been investigated. However, the heat treatment was the only
technique applied to the PSU membrane flat sheets, while other
investigation strategies were applied during the preparation of
PSU polymeric membranes.
Tension heating of the PSU was found to be an effective techni-
que for the reduction of the fiber diameter and the increase in the
pore size and surface porosity. Moreover, tension heating caused
higher compactness and smoother surface with improved me-
chanical properties and excellent chemical stability of the PSU
membrane. The morphology of the hollow-fiber PSU was
strongly affected by the air-gap length and ambient humidity after
the vapor-induced phase separation by the water vapor. Macro-
voids in the membranes disappeared, reappeared, and then re-
disappeared with the increasing air-gap length. The air-gap length
required for the suppression and re-suppression of macrovoids
decreased with the rise in relative humidity. Pluronic F127 and
DMMSAPS tended to increase the porosity of membranes as an
amphiphilic additive before inducing phase separation of the sol-
ution. As the additive concentration increased, both surface and
cross sections revealed their effects on the porous structure. For
membranes prepared using higher additive content at 5 wt % and
0.5 wt % of Pluronic F127 and DMMSAPS, respectively, PSU
membranes exhibited a noticeably more porous surface, since the
additives acted as a pore former.
In addition, innovative morphology control techniques
based on NIPS, such as phase separation micromolding and
www.ChemBioEngRev.de ª 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
the breath figure method, were developed to prepare mem-
branes with patterned structure. These techniques are promis-
ing because they showcase the potential to prepare membranes
for specific industrial and research applications. The main
parameters for controlling PSU membrane characteristics in a
sacrificial approach were investigated using PEI/NMP as the
coating solution and PSU/PVPK90/NMP as the support solu-
tion. It was concluded that an increase in PSU concentration
effectively suppressed the formation of concave defects in the
PSU surface. The increase in PVP concentration also signifi-
cantly decreased surface porosity. At the higher coagulant tem-
perature and thicker PEI coating, PSU membranes showed
higher permeability and larger pore size. The PSU membranes
impregnated with carbon nanotubes, multiwalled carbon nano-
tubes, silica nanoparticles, silver nanoparticles, and titanium
oxide nanoparticles had a significant effect on the morphologi-
cal characterization of the PSU membranes, surface hydrophi-
licity, and membrane performance. Furthermore, zeolite 4A
was added to the PSU membranes to balance out the tradeoff
between permeability and selectively, since the embedded zeo-
lites 4A caused a denser, rougher, negatively charged surface
with smaller pore sizes, which ensured a high rejection to BSA.
The addition of hydrophilic surfactant into the PSU polymeric
membrane had a highly favorable effect on the morphological
characteristics of PSU and allowed to increase the surface
porosity, surface hydrophilicity, and membrane permeability.
Acknowledgment
The authors are grateful for the financial support from the
Natural Science and Engineering Research Council of Canada
(NSERC). The assistance and facilities provided by the Depart-
ment of Chemical Engineering, Ryerson University, are also
highly appreciated.
The authors have declared no conflict of interests.
Amira Abdelrasoul is a Ph.D.
candidate and Research Assis-
tant under the supervision of
Prof. Huu Doan and Prof. Ali
Lohi at the Department of
Chemical Engineering at Ryer-
son University, Toronto. She
holds a Bachelor degree in
Chemical Engineering from
Alexandria University, Egypt,
and a Master of Science in
Chemical Engineering from
Kuwait University, Kuwait.
Her academic excellence, re-
search experience, and publication record in the field of
membrane technology has been recognized and she received
numerous scholarships, and various academic excellence
awards. Her research interests primarily focus on mem-
brane science and technology for water and wastewater
treatment, process modeling, simulation and optimization
of complex systems, and modern membrane technologies
for energy saving.
ChemBioEng Rev 2015, 2, No. 1, 22–43 40
 Abbreviations
Huu Dung Doan is a Profes-
sor at the Department of
AFM atomic force microscopy
Chemical Engineering at Ryer-
BSA bovine serum albumin
son University, Toronto. He
CNT carbon nanotubes
received his Bachelor of Engi-
CSLM confocal scanning laser microscopy
neering from Ryerson Univer-
DHC dirt-hold-capacity
sity, Toronto, his Master of
DMAc N,N-dimethylacetamide
Science from the University of
DMF dimethylformamide
Guelph, and his Ph.D. in
DMMSAPS 3-N,N-Dimethylmyristylammonio
Chemical Engineering from
propane-sulfonate
the University of Toronto. His
DWNT double-wall nanotubes
research interests include membrane filtration, especially
F127 Pluronic F-127 (Mw = 12 500 g mol–1)
fouling and modelling, mass transfer in a packed bed, and
HFM hollow fiber membrane
industrial wastewater treatment by electrochemical meth-
MF microfiltration
ods.
MMM mixed-matrix membrane
MWCO molecular weight cutoff
Ali Lohi is a Professor of MWNT multi-walled carbon nanotube
Chemical Engineering at Ryer- NIPS nonsolvent induced phase separation
son University, Toronto. His NMP N-methyl pyrrolidinone
research work covers topics in PDMS polydimethylsiloxane
the following areas: Process PEI polyetherimide
simulation/modeling; Optimi- PEG polyethylene glycol
zation of chemical processes; PSU polysulfone
Development of processes and PVDF polyvinylidene difluoride
models for reduction in energy PVP polyvinylpyrrolindone
consumption – remediation of SEM scanning electron microscopy
membrane fouling; Develop- SWNT single-wall nanotubes
ment of innovative and profi- TEM transmission electron microscopy
cient energy production pro- Tetronic 1107 ethylenediamine tetrakis(ethoxylated-block-
cesses; Utilization of waste propoxylate) tetrol
materials into new and value added products including bio- TIPS thermally induced phase separation
fuel and synthesis gas (syngas) from agriculture waste; TPGS D-a-tocopheryl polyethylene glycol succinate
Sequestration of CO2; Oil/gas processing and production; Tween 20 polyoxyethylene sorbitan monolaurate
Application of supercritical fluids as reaction medium; VIPS vapor-induced phase separation
Transport phenomena in environmental systems; Applica-
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