Journal of Membrane Science 327 (2009) 125–135

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Journal of Membrane Science

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

Characteristics, performance and stability of polyethersulfone ultrafiltration

membranes prepared by phase separation method using different
macromolecular additives
Heru Susanto a,b,∗ , Mathias Ulbricht a
a
Lehrstuhl für Technische Chemie II, Universität Duisburg-Essen, 45117 Essen, Germany
b
Department of Chemical Engineering, Universitas Diponegoro, Semarang, Indonesia

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

Article history: Polyethersulfone (PES) ultrafiltration (UF) membranes were prepared by non-solvent-induced phase
Received 30 June 2008 separation (NIPS) method using different macromolecular additives, polyvinylpyrrolidone (PVP),
Received in revised form 5 October 2008 poly(ethylene glycol) (PEG) and poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide)
Accepted 9 November 2008
(Pluronic® , Plu). Their effects on membrane structure and their stability in the polymer membrane matrix
Available online 24 November 2008
as well as the resulting membrane performance were systematically compared in order to determine the
additive that should be preferred. The investigated membrane characteristics include surface hydrophilic-
Keywords:
ity (by contact angle), surface charge (by zeta potential), surface chemistry (by FTIR spectroscopy), water
Ultrafiltration membrane
Membrane preparation
flux and rejection of macromolecular test substances. Visualization of membrane surface and cross-
Polyethersulfone section morphology was also done by scanning electron microscopy. The membrane performance was
Polyvinylpyrrolidone examined by investigation of adsorptive fouling and ultrafiltration using solution of bovine serum albu-
Poly(ethylene glycol) min as the model system. The stability of additive was examined by incubating the membrane in water
Poly(ethylene glycol)-b-poly(propylene (40 ◦ C) and sodium hypochlorite solution. Modification effects on membrane characteristic as well as per-
glycol)-b-poly(ethylene glycol) formance via blending membrane polymer and macromolecular additive were clearly observed. Overall,
Pluronic® the results suggest that Pluronic showed the best behavior in all respects, and, consequently, it should be
considered in practical applications.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction (PES) UF membranes are broadly manufactured for industrial appli-

Ultrafiltration (UF) has become the main focus as promising
separation tool in many industrial processes covering fraction-
ation and concentration steps in the food, in pharmaceutical
and biotechnological industries, in pure water production and
in water and wastewater treatments [1,2]. As consequence of
this increasing demand, efforts to improve UF process perfor-
mance are gaining more and more importance. In general, those
efforts include feed pretreatment, advanced membrane and mod-
ule design, and process condition optimization. However, in many
cases, the key for the performance of UF process is the mem-
brane itself. In this regard, three important characteristics for
achieving high performance UF membrane are high flux as well
as selectivity, low fouling and performance stability for long-term
operation.
Polymeric membranes prepared by non-solvent-induced phase
separation (NIPS) are still dominating commercially available UF
membranes. Among them, polysulfone (PSf) and polyethersulfone
∗ Corresponding author. Tel.: +49 201 1833066; fax: +49 201 1833147.
E-mail address: heru.susanto@uni-due.de (H. Susanto).
cations. Nevertheless, the hydrophobicity of those materials can
cause severe fouling problems; therefore, membrane modification
is usually done to increase the membrane resistance towards foul-
ing. Three different approaches including (i) membrane polymer
modification (pre-modification), (ii) blending of the membrane
polymer with a modifying agent (additive), and (iii) surface modifi-
cation after membrane preparation (post-modification) have been
proposed [3]. Even though blending technique can involve signif-
icant changes in composition of the casting solution, leading to
different membrane structure formed during the phase separa-
tion and, consequently, membrane properties can be quite different
from the unmodified reference material, it is simple and no addi-
tional step is needed during membrane manufacturing. In addition,
although stability of the modifying agent in the membrane matrix
can be a problem, the effect of hydrophilization of the polymer
membrane can clearly be observed. Therefore, this technique seems
to be of highest relevance from practical point of view. Polymeric
additives (usually hydrophilic polymers) in a casting solution are
also used in order to increase both pore size and porosity (pore-
forming agent) and to suppress macrovoid formation. However,
depending on the polymer membrane, solvent and NIPS conditions,
the opposite effect can also be observed.

0376-7388/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2008.11.025
126 H. Susanto, M. Ulbricht / Journal of Membrane Science 327 (2009) 125–135
Polyvinylpyrrolidone (PVP) and poly(ethylene glycol) (PEG)
have been intensively used as additives during preparation of
PES UF membranes by phase separation methods. The mecha-
nism of PES membrane formation with addition of PVP had well
been explained in many publications [4–8]. Addition of PVP into
PES–NMP (N-methyl-2-pyrrolidone) casting solution could sup-
press the macrovoid formation via decreasing the effect of delayed
demixing [7]. However, opposite effect, i.e., enlargement of the
macrovoid structure by addition of PVP into PES–DMF (dimethyl-
formamide) was also reported [8]. Increasing water permeability
as well as molecular weight cut off (MWCO) of PES membrane
by the addition of PVP was another observation [9]. Addition of
PVP to PES–NMP led to higher water permeability than without
PVP but the solute rejection (for PEG) was 15% lower than with-
out PVP. Moreover, it had been found that the characteristic and
performance of PES–PVP blend membranes were influenced by
the concentration and the molar mass of PVP [4,10,11]. The high-
est product permeation rate examined by using PEG solution was
obtained at PVP/PES weight ratio of unity [4]. Observed retention
coefficient as well as surface roughness increased with increasing
molar mass of PVP [11]. The effect of PVP content on the resulting
fouling behavior examined with protein was also investigated; the
presence of PVP could to some extent decrease degree of fouling of
the resulting membrane [12].
PEG with various molar masses was added during preparation
of PES UF membranes [13]. The performance of the resulting mem-
branes was influenced by both molar mass and concentration of
PEG. Membranes prepared with higher molar mass of PEG had
higher pure water permeation and larger pores. The water perme-
ation increased as concentration of PEG (400 and 600 g/mol) was
increased, while solute separation decreased. Apparently, an opti-
mum condition (high flux with acceptable solute rejection) was
achieved at PEG concentration of ∼10 wt%. In addition, differences
in surface morphology and roughness could also be detected. A sim-
ilar study was also performed by using PSf–NMP and PSf–DMAc
(dimethylacetamide) system [14]. The results showed that the
increase in PEG molar mass increased the membrane porosity lead-
ing to increase in water permeability for both systems. Liu et al. [15]
found an optimum PEG content in PES–NMP system for increas-
ing water permeability, and further increase in PEG content would
decrease the resulting water flux. Moreover, the addition of PEG
alone could not suppress macrovoid formation even at high concen-
tration. Only when relatively large amounts of water were added to
the dope solution, sponge-like membrane structure was obtained.
The effect of PEG/NMP ratio during preparation of PSf UF mem-
branes was investigated [16]. As the PEG content was increased
the pure water flux increased while the solute rejection would
decrease.
Recently, the group of Jiang has intensively proposed the use of a
triblock copolymer, poly(ethylene oxide)-b-poly(propylene oxide)-
b-poly(ethylene oxide) (Pluronic/Plu), as another attractive additive
for preparation of PES UF membranes [17–20]. They observed that
Pluronic could improve not only the flux but also the resistance
towards fouling. The resulting fouling resistance was significantly
influenced by Pluronic content and PEO chain length [19]. It was
reported that the apparent protein adsorption amount decreased
significantly with increasing the Pluronic content and reached
∼0 ␮g/cm2 at concentration of 10.5% [17]. By contrast, the protein
rejection and pure water flux were little influenced by the Pluronic
content. Very recently, the function of Pluronic as both hydrophilic
modifier and pore-forming agent has been confirmed [20].
In sum, three different macromolecular additives, i.e., PVP, PEG
and Plu, have frequently been used in the preparation of PES UF
membranes including a wide variety in preparation conditions
and polymer characteristics. Those additives determine the char-
acteristics as well as the performance of the resulting membrane,
and several cases have been reported where high performance
membranes could be obtained. However, considerable disagree-
ment was also observed among different reports. We believe that
this is because many parameters including characteristics of mem-
brane polymer (e.g., molar mass, concentration in casting solution),
solvent (e.g., solubility parameter, viscosity), additive (e.g., molar
mass, concentration), and preparation conditions (e.g., tempera-
ture, humidity) are involved. Therefore, it is hard to determine the
best additive that should be used in preparation of PES UF mem-
brane based on results of previous studies. Torrestiana-Sanchez
et al. [10] had briefly compared the use of PVP and PEG as non-
solvents during PES membrane preparation. However, the reported
data were very limited to water permeability and protein rejec-
tion. Other important parameters such as hydrophilicity, fouling
behavior and membrane stability have not yet been compared. In
the present study, the effects of those macromolecular additives
on characteristics, performance and stability of the resulting PES
UF membranes are systematically compared. All preparation condi-
tions, including composition of membrane casting solution as well
as molar mass of additive were maintained to be similar. Stability
study was included because the immobilization of hydrophilic addi-
tives in the polymeric membrane matrix is one of the critical issues
from a practical point of view. Thus, the best performing hydrophilic
macromolecular additive for preparation PES UF membranes will be
known based on the results of this work.
2. Experimental
2.1. Materials
Commercial PES (Ultrason E 6020 P) donated by BASF (Lud-
wigshafen, Germany) was used and dried at 120 ◦ C for at
least 4 h before use. N-methyl-2-pyrrolidone (NMP) was pur-
chased from Merck (Hohenbrunn, Germany). Polyvinylpyrrolidone
(MW ∼10,000 g/mol) was purchased from Serva Feinbiochemica
GmbH&Co. (Heidelberg, Germany). PEG (MW ∼10,000 g/mol) was
purchased from Fluka Chemie AG (Buchs, Germany) and Pluronic
F127 (Plu) (MW ∼12,600 g/mol) was purchased from BASF (Mount
Olive, NJ, USA). Bovine serum albumin (BSA) and sodium hypochlo-
rite were purchased from ICN Biomedicals, Inc. (California, USA)
and Sigma–Aldrich Chemie GmbH (Steinheim, Germany), respec-
tively. Dextrans T-4, T-15, T-35, T-100 and T-200 (the numbers
indicating molar mass in kg/mol) were from Serva Feinbiochemica
GmbH&Co. (Heidelberg, Germany). Potassium dihydrogen phos-
phate (KH2 PO4 ) and disodium hydrogen phosphate dihydrate
(Na2 HPO4 ·2H2 O) were purchased from Fluka Chemie AG (Buchs,
Germany). Potassium chloride (KCl), potassium hydroxide (KOH),
and hydrochloric acid (HCl), all of p.a. quality, were purchased from
Bernd Kraft GmbH (Duisburg, Germany). Nitrogen gas purchased
from Messer Griesheim GmbH (Krefeld, Germany) was ultrahigh
purity. Water purified with a Milli-Q system from Millipore was
used for all experiments.
2.2. Membrane preparation
PES (15 wt%) was dissolved in NMP (75%) with stirring, and
different additive with similar molar mass (PVP, PEG or amphiphilic
triblock copolymer Plu; 10 wt%) was added to the polymer solu-
tion. Attention should be given to PEG because it would not
dissolve in the NMP at ambient temperature. Therefore, slight
heating (∼45 ◦ C) was used during dissolution. This relative high
concentration of additive was aimed to see significant effects on
the resulting membrane. Polymer solution without an additive
was also prepared for control experiments. The homogenous
polymer solution was left without stirring until no bubbles were
 H. Susanto, M. Ulbricht / Journal of Membrane Science 327 (2009) 125–135
observed. The membranes were prepared by using Coatmaster
509 MC, Erichsen Testing Equipment. The polymer solution was
cast with a thickness of 200 m using a steel casting knife on a
glass substrate (casting speed 25 mm/s) and subjected to humid
air (RH = 50–60%) for 1 min. Thereafter, the proto-membrane was
solidified in a coagulation bath containing water (20 ± 1 ◦ C) for 1 h.
The resulting membranes were washed and soaked in the water
for 24 h before drying. Drying was sequentially done by immersing
in water, water/ethanol, ethanol and hexane.
2.3. Shrinkage measurements
Membrane shrinkage was calculated by measuring the area
of the initial film before solidification (“proto-membrane”) and
the membrane after solidification as well as after drying. These
areas were then compared to calculate degree of shrinkage (“plane
shrinkage”). In addition, membrane shrinkage was also calculated
based on the resulting membrane thickness and initial film thick-
ness (“vertical shrinkage”).
 
A1
degree of shrinkage (plane) (%) = 1− × 100
A0
 l1
 used to coat the outer surface of the sample with gold/palladium.
degree of shrinkage (vertical) (%) = 1− × 100
l0
where A0 is the area of proto-membrane, A1 is the area of membrane
after solidification or after drying and l0 and l1 are the thickness of
membrane before solidification and after drying, respectively. The
membrane thickness was measured by Coolant Proof micrometer
IP 65, Mutico Co., Japan.
2.4. Compaction, hydraulic permeability measurement,
adsorptive fouling and ultrafiltration procedures
All experiments were carried out by using a dead-end stirred cell
filtration system (Amicon cell model 8010 for compaction, hydraulic
permeability measurement and adsorptive fouling, model 8050 for
UF experiments) connected to a reservoir (∼450 mL) and pres-
surized by nitrogen from a gas tank. Membrane compaction was
performed by filtration of pure water at 450 kPa for 2 h. The flux
profile over time was monitored online gravimetrically. In all fur-
ther experiments, the membrane was firstly compacted for at
least 1 h (this time was enough to achieve steady flux, cf. Section
3.2). Hydraulic membrane permeability was measured at differ-
ent transmembrane pressures within the range 100–400 kPa and
at least five measurements from different membrane samples were
averaged.
For static adsorption experiments (adsorptive fouling), a solu-
tion of BSA (1 g/L, pH 7 in phosphate buffer) was added to the cell
and the outer membrane surface was exposed for 3 h without any
flux at a stirring rate of 3.1416 × 10−1 rad/s (300 rpm). Afterwards,
the solution was removed, and the membrane surface was rinsed
two times by filling the cell with pure water (5 mL) and shaking it
for 30 s. Water fluxes before and after exposure were measured at
the same pressure (300 kPa). The evaluation of membrane perfor-
mance was expressed in terms of the relative flux reduction, RFR
(Eq. (3)).
J0 − Ja
RFR (%) = × 100
J0
Ultrafiltration experiments at a constant transmembrane pres-
sure (300 kPa) were conducted using a BSA solution (0.1 g/L, pH 7 in
phosphate buffer) as the feed. The balance was connected to the PC,
the weight of permeate was recorded online, and the flux was cal-
culated. The permeate flux profile over time was investigated. BSA
concentrations were determined by measuring its UV absorbance
at 280 nm. The apparent BSA rejection was calculated using Eq. (4).
127
2.5. Rejection measurement
Rejection tests were conducted with a five component mixture
of dextrans with molar mass ranging from 4 to 200 kg/mol at a
total concentration of 1 g/L. Experiments were performed using a
dead-end stirred filtration system (Amicon cell model 8050, Mil-
lipore; cf. Section 2.4) at a pressure of 100 kPa and a stirring rate
of 300 rpm. Around 10 mL of permeate was collected. The com-
positions of dextran mixtures in the permeate (Cdownstream ) and
feed/retentate (Cupstream ) sides of membrane were analyzed using
gel permeation chromatography (GPC). The apparent rejection for
each molar mass was calculated using the following equation:
Cdownstream
R=1− (4)
Cupstream
2.6. Membrane morphology
The top surface and cross-section morphology of the mem-
branes were observed by using a Quanta 400 FEG (FEI)
environmental scanning electron microscope (ESEM) at standard
(1)
high-vacuum conditions. A K 550 sputter coater (Emitech, U.K.) was
(2) For cross-section analysis, the membranes were broken in liquid
nitrogen and sputtered for 1.5 min, while for analysis of outer mem-
brane surface, sputtering was done for 0.5 min.
2.7. Contact angle (CA)
Sessile drops static CA was measured using an optical con-
tact angle measurement system (OCA 15 Plus; Dataphysics GmbH,
Filderstadt, Germany). Five microlitres of water was dropped on the
membrane surface from a microsyringe with a stainless steel nee-
dle in room temperature (21 ± 1 ◦ C). At least seven measurements
of drops at different locations were averaged to obtain CA for one
membrane sample.
2.8. Zeta potential (ZP)
The membrane surface charge was investigated by an outer
surface streaming potential measurement. Experiments were car-
ried out in a flat-sheet tangential flow module described in detail
in previous study [21]. Before measurement, the membrane was
equilibrated by soaking in 0.001 mol/L KCl solution. The stream-
ing potentials of membranes were measured using 0.001 mol/L KCl
solution within the pH range 3–10 and at a temperature of 25 + 1 ◦ C.
The ZP was calculated using the Helmholtz–Smoluchowski equa-
tion.
2.9. Surface chemistry
The membrane surface chemistry was analyzed by using the
instrument Varian 3100 Fourier transform infrared spectroscopy
(FTIR) Excalibur series. A total of 64 scans were performed at a
resolution of 4 cm−1 and the temperature of 21 + 1 ◦ C. The Varian’s
Resolution Pro 4.0 was used to record the membrane spectra versus
the corresponding background spectra.
(3)
2.10. Stability test
The stability of macromolecular additive in polymer membrane
matrix was examined by incubating membrane samples in water
(20 and 40 ◦ C) and sodium hypochlorite solution (active chlorine
concentration 400 mg/L) for up to 10 days. Water is usually used
for membrane washing before chemical cleaning will be done.
Hypochlorite solution had been known as one of the most popular
128 H. Susanto, M. Ulbricht / Journal of Membrane Science 327 (2009) 125–135

Fig. 1. “Plane” membrane shrinkage after coagulation and drying for different mem-
branes. PES(only), PES–PVP, PES–PEG and PES–Plu are membranes prepared without
an additive, with PVP, with PEG and with Pluronic additives, respectively. The error
bars represent standard deviation.
chemical cleaning agents to remove irreversible fouling [22–24].
Surface chemistry (by FTIR), surface hydrophilicity (by CA) and
water flux measurements were used to investigate changes in mem-
brane characteristics and transport property. The experiments were
done by using a different membrane. In water flux stability study,
the pure water flux was firstly measured (before soaking) and
membranes were then soaked in hypochlorite solution in closed
containers for a certain number of days. Thereafter, the membrane
was rinsed and the water flux was again measured.
3. Results and discussions
3.1. Shrinkage and membrane thickness
Fig. 2. Water flux profile over time during compaction at pressure of 450 kPa.
solidification may be able to explain [26,27]. It is clearly seen that
different macromolecular additive would result in different poly-
mer characteristics and consequently, polymer contraction would
also be different. It should also be noted that the total polymer
concentration for PES(only) was significantly smaller than the oth-
ers and consequently, lower viscosity and faster solvent exchange
should be obtained. Difference in miscibility between PES and addi-
tive for different additives used might also contribute. We have
tried to investigate the miscibility by using differential scanning
calorimetry (DSC). However, clear explanation could not be drawn
from the resulting data. Residual solvent in the sample might have
influence on the resulting DSC thermogram. Such phenomena seem
to be found also in previously reported literature [18]. Further anal-
ysis of this miscibility is now currently under investigation. Overall,
PES–Plu and PES–PEG membranes showed smaller shrinkage than
both PES(only) and PES–PVP membranes.

Understanding of membrane shrinkage will give information

3.2. Membrane compaction, water permeability and membrane
for predicting the area of a non-supported asymmetric membrane
rejection
product but not for a supported asymmetric membrane. High
shrinking tendency will result in tensions within the membrane,
Compaction – a compression of the membrane structure under
and this can have influence on structure of the resulting mem-
a transmembrane pressure difference causing a decrease in mem-
branes. It was reported that shrinkage had effect on membrane
brane permeability due to mechanical deformation of the solid
porosity [25]. Fig. 1 and Table 1 show the plane and the vertical
polymer – is a common phenomenon during application of
shrinkages, respectively.
polymeric membranes [28,29]. In this compaction study, the mem-
As clearly seen in Fig. 1 and Table 1, decreases in membrane
branes were pressurized at high pressure (450 kPa) for 2 h.
area and thickness indicate that the PES film shrank not only in the
Fig. 2 shows an example of the water flux profile over time
plane view but also in the vertical direction. In plane view, PES–PVP
during compaction for all membranes. Indeed, gradual decrease
membrane showed the highest degree of shrinkage (25%) followed
in flux over the duration of compaction time was observed for all
by PES (only). The highest shrinkage of PES–PVP might contribute
membranes, and flux reached a steady value after ∼60 min of com-
to smaller surface porosity as noticed by its smallest water perme-
paction. The steady fluxes were ∼80%, ∼35%, ∼40% and ∼60% of the
ability among the PES membranes prepared with an additive (cf.
initial flux for PES(only), PES–PVP, PES–PEG and PES–Plu, respec-
Section 3.2). Although the membranes have been dried by exchange
tively. Interestingly, the membrane prepared by using Pluronic
with organic non-solvent (for PES) method, shrinkage after drying
as the additive had initially lower flux than the membrane pre-
could still be observed. Different with plane view, all membranes
pared using PEG as the additive, but beyond 30 min duration of
prepared using an additive showed similar degree of shrinkage in
compaction it showed higher flux. Because all membranes had
vertical view. Even though the reason behind this shrinkage phe-
asymmetric structure (cf. SEM images), the compaction at high
nomenon is still not clearly understood, polymer contraction upon
pressure would cause densification of the more porous support
layer leading to a thickening of the skin layer (selective barrier).
Table 1 Consequently, thicker membrane would result in lower flux. Such
Membrane thickness and the resulting “vertical” shrinkage after drying (polymer
phenomenon had been observed in the previous reported literature
solution has been cast with 200 ␮m thickness).
[28,30].
No. Membrane Thickness (␮m) Degree of shrinkage (%) Table 2 shows the hydraulic membrane permeability measured
1 PES(only) 98 ± 4 51 after 1 h of compaction. The hydraulic permeability of the wet
2 PES–PVP 130 ± 4 35 membranes (never dried) is also included. The membrane prepared
3 PES–PEG 135 ± 5 32 without an additive showed the highest hydraulic permeability
4 PES–Plu 143 ± 6 29
for both conditions. It is seen that drying process significantly
 H. Susanto, M. Ulbricht / Journal of Membrane Science 327 (2009) 125–135
Table 2
Hydraulic membrane permeability measured after 1 h compaction.
No. Membrane Lp (L/m2 h kPa) after drying Lp (L/m2 h kPa) before drying
1 PES 0.251 ± 0.16 1.05 ± 0.09
2 PES–PVP 0.066 ± 0.02 1.320 ± 0.06
3 PRS–PEG 0.101 ± 0.02 1.421 ± 0.03
4 PES–Plu 0.131 ± 0.04 1.178 ± 0.05
decreased the hydraulic permeability of all membranes. The flux
reductions after solvent exchange drying were ∼76%, ∼95%,∼93%
and ∼88% for PES(only), PES–PVP, PES–PEG and PES–Plu mem-
branes, respectively (drying without solvent exchange resulted in
much greater flux reductions). The absence of impregnation may
contribute to this very large decrease in flux after drying but it
should not be the only reason. Nevertheless, the effect of drying
on membrane performance was beyond the scope of this paper.
Because all relative flux reductions showed similar trend; all fur-
ther experiments were performed and discussed by using dried
membranes.
In general, addition of a hydrophilic polymer can facilitate liquid
demixing because the system will be closer to phase separation on
the one hand, and slow down phase separation by hindering non-
solvent inflow to the polymer–solvent mixture (delayed demixing)
due to higher viscosity on the other hand. By contrast, the poly-
mer solution without an additive would facilitate faster solvent
exchange due to much lower viscosity. It was reported that addition
of 10% of PVP or PEG into 20% of PES in NMP solution increased the
casting solution viscosity up to more 200% (from 0.70 to 2.75 Pa s)
[10]. In this work, the hydraulic permeability data of wet mem-
branes showed that addition of a hydrophilic polymer increased the
resulting water flux suggesting that the effect of delayed demixing
was less significant compared to the effect of instantaneous liquid
demixing.
In order to quantify the pore size and its distribution of selective
barrier, the rejection of polydisperse macromolecular test sub-
stances (dextran) was then measured. Fig. 3 shows that the addition
of a macromolecular modifier into polymer solution changed the
rejection curve of the membrane. As shown in Fig. 3, the mem-
brane prepared without an additive had a steeper separation curve
implying that the pore size distribution is narrower than for the
membranes prepared with an additive. In addition, it had smaller
MWCO but showed the greatest permeate flux during rejection
experiment (data not shown) and water flux (cf. above). It is impor-
tant to mention that repeating experiments (with selection criteria
for the membrane samples, i.e., only membranes that have water
permeability in the range of 15% relative to the average values were
Fig. 3. Rejection curve of membranes determined by using a dextran mixture solu-
tion with total concentration of 1 g/L (as the feed) and at a pressure of 100 kPa.
129
chosen) showed that most of the results showed similar trends
with Fig. 3 and the standard deviations of MWCO were within the
range 15–30%. The possible reason for this observation would be
that even though the PES(only) membrane had smaller MWCO it
had a higher pore density than the membranes prepared with an
additive.
Comparing the membranes prepared with an additive, it is
clearly shown that all membranes showed similar rejection curve
trend. The hydraulic membrane permeability, rejection and perme-
ate flux data suggest that the PES–Plu membrane had either the
highest pore density or largest pore size leading to the highest sur-
face porosity among the membranes prepared with an additive.
Comparing PES–PVP and PES–PEG, it is shown that PES–PEG had
higher hydraulic permeability. This observation agrees with result
reported by Torrestiana-Samschez et al. [10].
3.3. Membrane morphology
Membrane surface morphology as well as cross-section struc-
ture was visualized by using SEM. It is important to mention that
the SEM observation for membrane surface was repeated for every
membrane and similar image was obtained for most of samples. As
presented in Fig. 4, all membranes had asymmetric structure con-
sisting of a thin fine porous selective barrier and a much thicker
porous sub-structure. The phenomena behind the formation of this
typical structure had been explained in many previous publications
[6,7]. Cross-section images support the results of membrane thick-
ness measurement (cf. Section 3.1), except for PES–PVP membrane.
It seemed that part of PES–PVP membrane disappeared during sam-
ple preparation. Visualization of surface morphology showed that
the membrane surface had fine pore structure with dimensions in
the nanometer range (<10 nm). It is clearly seen that PES–PVP had
the roughest surface morphology (it should be noted that the drying
process has been done by non-solvent exchange method, thereby
collapse of the pore structure should be minimized). Quantification
of surface roughness performed by Ochoa et al. [11] showed that
the addition of PVP in preparation of PES UF membranes increased
the surface roughness. Comparing surface images of PES(only) and
PES–Plu membranes, it appears that the PES–Plu membrane had
larger pore size than PES(only). Nevertheless, it seems that the pore
density of PES(only) membrane is higher than that of the PES–Plu
membrane. Thus, smaller pore size but higher pore density for
PES(only) compared to PES–Plu supports the previous discussion
of hydraulic permeability and rejection curve results.
3.4. Membrane surface hydrophilicity
As clearly seen in Table 3, PES membrane without an additive
had lower CA (∼65◦ ) than typically measured for non-porous PES
film (∼76◦ ) [31]. Porous structure in the outer membrane surface
would be the reason for this difference. Therefore, care should be
taken to interpret the CA results because the value is influenced not
only by membrane material but also by surface porosity. Indeed,
such effect is observed by comparing the CA data of PES(only),
PES–PEG and PES–Plu membranes. The membrane prepared with-
out an additive showed similar CA with the membranes prepared
Table 3
Static water contact angle, measured by sessile drop method, of membranes pre-
pared using different additives.
No. Membrane Contact angle (◦ )
1 PES(only) 64.5 ± 3.3
2 PES–PVP 64.1 ± 2.9
3 PES–PEG 54.1 ± 1.9
4 PES–Plu 61.7 ± 2.8
130 H. Susanto, M. Ulbricht / Journal of Membrane Science 327 (2009) 125–135

Fig. 4. SEM images of the cross-section and membrane surface morphology: from the top to the bottom panel: PES(only), PES–PVP, PES–PEG and PES–Plu, respectively.

with a hydrophilic additive (PES–PVP and PES–PEG). This could
be explained because the PES(only) membrane had higher surface
porosity as noticed by its higher permeability. Comparing the CA
data of PES–PEG and PES–Plu membranes suggests that the contri-
bution of hydrophobic part of block copolymer in Pluronic could be
observed (note that these membranes had similar rejection curve,
cf. Fig. 3). It is interesting to note that PES–PEG membrane had
significantly lower CA compared to other membranes indicating
that this was the most hydrophilic membrane, while PES–PVP and
PES–Plu membranes showed similar value.
 H. Susanto, M. Ulbricht / Journal of Membrane Science 327 (2009) 125–135 131

Fig. 7. FTIR spectra of membranes prepared with different macromolecular addi-

Fig. 5. Zeta potentials as a function of pH calculated from the tangential streaming tives.
potential of the outer surface of different membranes (at 0.001 mol/L KCl).

mary amide stretch was observed for the membrane prepared with
3.5. Membrane surface charge
addition of PVP. By contrast, no additional peak was observed for
the membranes prepared with addition of PEG or Plu. The reason
Zeta potential was measured in order to get information on sur-
for this result would be overlapping bands of the strongest bands
face charge of the membranes. As presented in Fig. 5, all membrane
for PEG and Plu (ether) with bands for PES (ether; cf. Figs. 6 and 7).
surfaces had a negative charge over the entire pH range studied, and
Indeed, a significant increase in transmittance at ∼1105 cm−1 , due
the absolute values decreased to acidic pH range (cf. Ref. [21] for the
to additional intensity of C–O bond stretch (from PEG and Plu) was
reasons behind this phenomenon). The addition of a macromolecu-
observed and this confirms the presence of the additives in the
lar modifier into polymer solution obviously changed the effective
membrane polymer matrix. Overall, the IR spectra data indicate
surface charge of the PES membrane. Nevertheless, a linear decrease
that changes in surface chemistry were detected after addition of
in ZP with increasing pH solution for all membranes reflects typ-
the macromolecular modifiers to the membrane polymer solution.
ical behavior of a surface that has a negative charge due to anion
adsorption from the solution. Both PEG and Plu decreased the sur-
face charge toward smaller absolute value. By contrast, addition of 3.7. Membrane performance based on adsorptive fouling and
PVP increased the negative charge of membrane. These indicated ultrafiltration
that adsorption of anions (hydroxyl, chloride) from the solution was
more significant for PES–PVP than for the other membranes. The effect of additive on membrane performance was inves-
tigated with respect to adsorptive fouling and ultrafiltration.
Adsorptive fouling was studied by exposing the outer membrane
3.6. Membranes surface chemistry
surface (selective barrier side) to protein (BSA) feed solution. The
relative water flux reduction (RFR) was used to identify the extent
Figs. 6 and 7 show the IR spectra of macromolecular additives
of adsorptive fouling. As clearly seen in Fig. 8, the membranes pre-
used for membrane preparation and of the resulting membranes,
pared with an addition of hydrophilic modifier showed significantly
respectively. As expected, all membranes showed typical spectra
higher resistance towards adsorptive fouling than the membrane
of PES, i.e., aromatic bands at 1578 and 1485 cm−1 from the ben-
prepared without an additive as noticed by their much lower RFR. It
zene ring and C C bond stretch and aromatic ether band around
1240 cm−1 . A new significant peak at 1678 cm−1 assigned to a pri-

Fig. 8. Relative flux reduction after static adsorption using BSA (1 g/L in phosphate
Fig. 6. FTIR spectra of the macromolecular additives used. buffer 0.05 M, pH 7, 3 h exposure). The error bars represent standard deviation.
132 H. Susanto, M. Ulbricht / Journal of Membrane Science 327 (2009) 125–135
Fig. 9. Normalized flux during ultrafiltration of BSA solutions (0.1 g/L in phosphate buffer 0.05 M, pH 7) at a transmembrane pressure of 300 kPa. Water fluxes after external
cleaning with water, relative to initial water flux are also included.
should be kept in mind that the effects of adsorptive fouling depend
also on the barrier pore size, and the highest flux reductions were
found for matching pores and solute sizes (cf. [31]); considering
that the pore size distributions were different but still in the same
range (cf. Fig. 3), the hydrophobicity of PES seemed to have an addi-
tional impact on RFR. This suggests that blending of hydrophilic
macromolecular additive with membrane polymer could indeed
significantly increase the hydrophilicity of the resulting membrane.
PES–PEG membrane showed the lowest RFR among the membranes
prepared with an additive. This result can be explained by the high-
est hydrophilicity of this membrane (cf. Table 3). It should be noted
that the protein in solution had negative charge and if electro-
static interactions would play a dominant role, PES–PVP membrane
should have the lowest RFR (cf. Fig. 5).
Lower adsorptive fouling for PES membranes prepared with an
additive compared to PES(only) membrane was also observed from
ZP measurements after adsorptive fouling (cf. Fig. 5). The change in
ZP after adsorptive fouling indicates the presence of protein on the
membrane surface. The much larger change for PES(only) than for
PES–Plu suggests that the degree of adsorptive fouling was higher
for PES(only) membrane. The positive value of ZP for pH values <4.9
after adsorptive fouling can be explained by considering the IEP of
the BSA (pH ∼4.8), i.e. an excess of positive surface charge has been
introduced via the protein.
To investigate ultrafiltration performance, dead-end stirred
ultrafiltration was performed with constant transmembrane pres-
sure (300 kPa). The results are presented in terms of permeate
flux relative to initial water flux (Fig. 9). It was observed that per-
meate flux dropped rapidly in the beginning of filtration for all
membranes. On the one hand, this phenomenon indicates that
concentration polarization has taken place. On the other hand,
difference in flux profile for the membranes having similar rejec-
tion curve (PES–PVP, PES–PEG and PES–Plu, cf. Fig. 3) suggests
that fouling also contributed to the permeate flux decline. Water
flux measurements after external cleaning using water confirmed
that both reversible and irreversible fouling have occurred. Fur-
thermore, higher increase in water flux after external cleaning
compared to permeate flux for membranes prepared with an addi-
tive implies that reversible fouling was more significant for those
membranes than for the membrane prepared without an addi-
tive. It is interesting to note that the PES(only) membrane had the
highest permeability and a distinctly different pore size distribu-
tion (significantly larger sieving for dextran molar masses below
about 50 kDa—which corresponds to the size of BSA, cf. Fig. 3).
The higher observed BSA rejection could then be due to fouling
(cf. below).
Table 4
Apparent protein rejection.
No. Membrane Rejection (%)
1 PES(only) 87
2 PES–PVP 71
3 PES–PEG 75
4 PES–Plu 72
Indeed, the presence of hydrophilic macromolecular additive
increased the normalized flux indicating that higher resistance
towards fouling has been obtained. The membrane prepared with-
out an additive had permeate flux of only ∼30% relative to the
initial water flux, whereas the PES–Plu membrane had the high-
est permeate flux (more than 70%). Of course, the highest initial
flux of the membrane without an additive also contributed to the
lowest normalized flux but the effect of hydrophilic modifier was
quite clear. Interestingly, at the beginning of filtration PES–PEG
membrane had higher normalized flux than PES–Plu membrane
but further decrease with filtration time was more significant. The
possible reason for this phenomenon would be the stability of the
additive in the matrix polymer membrane (cf. Section 3.8).
Rejection data presented in Table 4 show that the PES membrane
prepared without an additive had the highest protein rejection
while all membranes prepared with an additive showed similar
protein rejection. This result is in good agreement with rejection
curve if the molar mass of BSA is fitted. In general, performance
test showed that the membrane prepared with addition of Pluronic
as modifier agent showed the best performance, i.e., the lowest flux
decline and similar rejection could be obtained.
3.8. Stability test study
Because cleaning cannot be avoided in practical application, the
performance of membrane prepared with a hydrophilic additive
will strongly depend on the stability of the additive in the mem-
brane polymer matrix during membrane cleaning. In this work, the
stability of hydrophilic additive in water (20 and 40 ◦ C) and sodium
hypochlorite solution was investigated. Surface chemistry by FTIR,
contact angle and transport property by water flux were used as
indicators to evaluate the membrane stability.
Fig. 10 shows that no change in CA was observed for the
PES(only) membrane after soaking in water (40 ◦ C), while slight
decrease was observed after incubating in NaOCl solution. Increas-
ing porosity as noticed by increase in water flux (cf. Fig. 12)
would be the possible reason for this change. For the mem-
 H. Susanto, M. Ulbricht / Journal of Membrane Science 327 (2009) 125–135 133

branes prepared with an additive, soaking in the water 40 ◦ C By contrast, after immersion in sodium hypochlorite solution,
did not change the CA of PES–PVP and PES–Plu membranes significant increase in flux was observed for all membranes
while soaking in NaOCl slightly decreased. Decrease in CA via including the membrane prepared without an additive. In this
increasing porosity seemed to be dominant compared to increase case, PES degradation by NaOCl leading to higher porosity was
in CA via extracting hydrophilic additive during immersing in more dominant rather than extracting of hydrophilic additive.
NaOCl solution. Indeed, significant increase in CA was observed ZP measurement after soaking in NaOCl solution (the same con-
for PES–PEG after incubating in water and NaOCl solution even centration as in stability test) supports this observation. The
only after 2 days of incubating. This indicates that the stabil- negative charge of both PES(only) and PES–Plu membranes sig-
ity of PEG in the membrane polymer matrix was quite low. nificantly increased after soaking. The ZP at pH 9.5 decreased
Consequently, hydrophilic character of the resulting membrane from −11.5 to −22 mV and from −6.1 to −11.5 for PES(only) and
would easily be reduced even when only water is used for clean- PES–Plu membranes, respectively. Chain scission of the PES C–S
ing. Similar results with respect to stability in water at 40 ◦ C bond by attack of NaOCl yielding finally sulfonic acid groups
were found during stability test in water at 20 ◦ C (data not has been evoked [24], while extraction or reduced swelling
shown). of hydrophilic macromolecular additive has also been reported
As presented in Fig. 11, slight decrease in IR absorbance for the [23,32,33].
introduced functional additive (cf. Section 3.6) was observed for
all additives used after soaking in both water and NaOCl solution.
This indicates that none of the additives was completely stable in
the matrix polymer membrane. However, irrespective this loss, sig-
nificant surface modification could still be observed as noticed by
either the appearance of new peak (for PES–PVP) or increase in
transmittance (for PES–PEG and PES–Plu) even after soaking for 10
days in all studied potential cleaning agents.
Fig. 12 shows the flux stability of the membranes dur-
ing incubating. It is clearly seen that flux of all membranes
did not change after incubating in water (data for 20 ◦ C are
not shown). Slight decreases in flux for PES–PVP and PES–PEG
membranes were still within the range of experimental error.

Fig. 10. Stability test investigated by measuring the contact angle as a function of
incubating time. Soaking the membranes in water (20 ◦ C) resulted in similar effect Fig. 11. Stability test investigated by measuring the IR absorbance of functional
with soaking in water 40 ◦ C. additive as a function of incubating time.
134 H. Susanto, M. Ulbricht / Journal of Membrane Science 327 (2009) 125–135
Fig. 12. Stability test investigated by measuring the water flux as a function of incu-
bating time. Soaking the membranes in water (20 ◦ C) yielded similar effect with
soaking in water 40 ◦ C.
In general, in this stability study, PES–Plu membrane showed
the best stability followed by PES–PVP among the membranes pre-
pared with an additive event though slight removal observed from
surface chemistry by FTIR could still be detected. The reason for
this phenomenon would be that the hydrophobic part of Pluronic
enhances the PES–additive interaction. Not only entanglement but
also hydrophobic–hydrophobic interactions may occur. The possi-
ble interaction of Pluronic in PES polymer membrane matrix was
described by Jiang et al. [17,20]. The interaction between PES and
PVP has been identified through investigation of viscoelastic behav-
ior of their polymer mixtures [4]. The authors proposed that the
interaction between PES and PVP could be either between NH–C O
groups in PVP and O S O groups in PES or between side cyclic
groups of PVP and aromatic ring of PES.
4. Conclusions
The characteristics, performance and stability of PES membranes
prepared by NIPS with three different macromolecular additives,
i.e., PVP, PEG and Plu, have been investigated. The characteristic
of additive and the preparation conditions were maintained to be
similar so that the performance of those additives can be fairly com-
pared. Indeed, the presence of those macromolecular additives in
membrane polymer matrix as noticed by FTIR data significantly
determined the characteristic as well as performance of the result-
ing membranes. This observation was confirmed by investigation
of PES membrane prepared without an additive as comparison.
The PES membrane prepared with addition of Pluronic (PES–Plu)
showed the highest hydraulic permeability among the membranes
prepared with macromolecular additives, whereas the rejection
curves examined using mixture of dextrans were similar for all
three modified membranes. All membranes had negative surface
charge within the entire pH range studied. Surface hydrophilic-
ity measured with CA indicates that the PES–PEG membrane was
the most hydrophilic membrane; nevertheless, the stability of that
macromolecular additive within the membrane polymer matrix
was the most crucial problem. Performance evaluation via inves-
tigation of adsorptive fouling and ultrafiltration using BSA suggests
that PES–PEG membrane showed the lowest RFR after static adsorp-
tion followed by PES–Plu. Ultrafiltration experiments demonstrated
that the antifouling effects of PES–Plu were the most efficient
at similar protein rejection: permeate flux during ultrafiltration
using the PES–Plu was much higher than using the PES–PEG and
the PES–PVP membranes, and more than 70% of the initial water
flux could be recovered after UF just by external cleaning with
water. Overall, performance test and stability study suggest that
the membrane prepared with the addition of Pluronic as modifier
agent showed the best performance as well as the best stability;
therefore, it should be considered as additive in practical applica-
tions.
Acknowledgements
The authors thank Dieter Jacobi (Technische Chemie, Universität
Duisburg Essen) for the GPC analysis and Smail Boukercha (Anor-
ganische Chemie, Universität Duisburg Essen) for his contribution
on SEM observation. We also thank BASF (Germany) for supplying
the PES polymer.
References
[1] M. Cheryan, Ultrafiltration and Microfiltration Handbook, Technomic Publish-
ing Company Inc., Pennsylvania, 1998.
[2] R.W. Baker, Membrane Technology and Applications, 2nd ed., John Wiley & Sons,
Ltd., Chichester, 2004.
[3] H. Susanto, M. Ulbricht, Polymeric membranes for molecular separations, in:
E. Drioli, L. Giorno (Eds.), Membrane Operations. Innovative Separations and
Transformations, Wiley–VCH, Weinheim, in press.
[4] L.Y. Lafreniere, F.D.F. Talbot, T. Matsuura, S. Sourirajan, Effect of polyvinylpyrroli-
done additive on the performance of polyethersulfone ultrafiltration
membranes, Ind. Eng. Chem. Res. 26 (1987) 2385.
[5] R.M. Boom, H.W. Reinders, H.H.W. Rolevink, Th. van den Boomgaard, C.A.
Smolders, Equilibrium thermodynamics of a quaternary membrane-forming
system with two polymers. I. Experiments, Macromolecules 27 (1994)
2041.
[6] M. Wienk, R.M. Boom, M.A.M. Beerlage, A.M.W. Bulte, C.A. Smolders, Recent
advances in the formation of phase inversion membranes made from amor-
phous or semi-crystalline polymers, J. Membr. Sci. 113 (1996) 361.
[7] R.M. Boom, I.M. Wienk, Th. Van den Boomgaard, C.A. Smolders, Microstruc-
tures in phase inversion membranes. Part 2. The role of a polymeric additive, J.
Membr. Sci. 73 (1992) 277.
[8] H.T. Yeo, S.T. Lee, M.J. Han, Role of polymer additive in casting solution in prepa-
ration of phase inversion polysulfone membranes, J. Chem. Eng. Jpn. 33 (2000)
180.
[9] D.B. Mosqueda-Jimenez, R.M. Narbaitz, T. Matsuura, G. Chowdhury, G. Pleizier,
J.P. Santerre, Influence of processing conditions on the properties of ultrafiltra-
tion membranes, J. Membr. Sci. 231 (2004) 209.
[10] B. Torrestiana-Sanchez, R.I. Ortiz-Basurto, E.B. Fuente, Effect of nonsolvents on
properties of spinning solutions and polyethersulfone hollow fiber ultrafiltra-
tion membranes, J. Membr. Sci. 152 (1999) 19.
[11] N.A. Ochoa, P. Pradanos, L. Palacio, C. Pagliero, J. Marchese, A. Hernandez, Pore
size distributions based on AFM imaging and retention of multidisperse poly-
mer solutes: characterisation of polyethersulfone UF membranes with dopes
containing different PVP, J. Membr. Sci. 187 (2001) 227.
[12] J. Marchese, M. Ponce, N.A. Ochoa, P. Pradanos, L. Palacio, A. Hernandez, Foul-
ing behaviour of polyethersulfone UF membranes made with different PVP, J.
Membr. Sci. 211 (2003) 1.
[13] A. Idris, N.M. Zain, M.Y. Noordin, Synthesis, characterization and performance of
asymmetric polyetehrsulfone (PES) ultrafiltration membranes with polyethy-
lene glycol of different molecular weights as additives, Desalination 207 (2007)
324.
[14] B. Chakrabarty, A.K. Ghoshal, M.K. Purkait, Effect of molecular weight of PEG
on membrane morphology and transport properties, J. Membr. Sci. 309 (2008)
209.
 H. Susanto, M. Ulbricht / Journal of Membrane Science 327 (2009) 125–135
[15] Y. Liu, G.H. Koops, H. Strathmann, Characterization of morphology controlled
polyethersulfone hollow fiber membrane by the addition of polyethylene
glycol to the dope and bore liquid solution, J. Membr. Sci. 223 (2003)
187.
[16] J.H. Kim, K.H. Lee, Effect of PEG additive on membrane formation by phase
separation, J. Membr. Sci. 138 (1998) 153.
[17] Y. Wang, T. Wang, Y. Su, F. Peng, H. Wu, Z. Jiang, Remarkable reduction of irre-
versible fouling and improvement of permeation properties of polyethersulfone
ultrafiltration membrane by blending with Pluronic F127, Langmuir 21 (2005)
11856.
[18] Y. Wang, Y. Su, Q. Sun, X. Ma, X. Ma, Z. Jiang, Improved permeation performance
of Pluronic F127-polyethersulfone blend ultrafiltration membranes, J. Membr.
Sci. 282 (2006) 44.
[19] Y.Q. Wang, Y.L. Su, X.L. Ma, Q. Sun, Z.Y. Jiang, Pluronic polymers and
polyethersulfone blend membranes with improved fouling resistant ability and
ultrafiltration performance, J. Membr. Sci. 283 (2006) 440.
[20] W. Zhao, Y. Su, C. Li, Q. Shi, X. Ning, Z. Jiang, Fabrication of antifouling polyether-
sulfone ultrafiltration membranes using Pluronic F127 as both surface modifier
and pore-forming agent, J. Membr. Sci. 318 (2008) 405.
[21] H. Susanto, M. Ulbricht, Influence of ultrafiltration membrane characteristics
on adsorptive fouling with dextrans, J. Membr. Sci. 266 (2005) 132.
[22] S. Rouaix, C. Causeserand, P. Aimar, Experimental study of the effects of
hypochlorite on polysulfone membrane properties, J. Membr. Sci. 277 (2006)
137.
[23] I.M. Wienk, E.E.B. Meuleman, Z. Borneman, A. van den Boomgaard, C.A. Smol-
ders, Chemical treatment of membranes of a polymer blend: mechanism of the
reaction of hypochlorite with poly(vinylpyrrolidone), J. Polym. Sci. A: Polym.
Chem. 33 (1995) 49.
[24] E. Arkhangelsky, D. Kuzmenko, V. Gitis, Impact of chemical cleaning on proper-
ties and functioning of polyethersulfone membranes, J. Membr. Sci. 305 (2007)
176.
135
[25] L. Wu, J. Sun, Q. Wang, Poly(vinylidine fluoride)/polyethersulfone blend mem-
branes: effect of solvent sort, polyethersulfone and polyvinylpyrrolidone
concentration on their properties and morphology, J. Membr. Sci. 285 (2006)
290.
[26] P. Menut, Y.S. Su, W. Chinpa, C. Pochat-Bohatier, A. Deratani, D.M. Wang, P.
Huguet, C.Y. Kuo, J.Y. Lai, C. Dupuy, A top surface liquid layer during mem-
brane formation using vapour-induced phase separation (VIPS)—evidence and
mechanism of formation, J. Membr. Sci. 310 (2008) 278.
[27] T.A. Tweddle, O. Kutowy, W.L. Thayer, S. Sourirajan, Polysulfone ultrafiltration
membranes, Ind. Eng. Chem. Prod. Res. Dev. 22 (1983) 320.
[28] V.E. Reinsch, A.R. Greenberg, S.S. Kelley, R. Peterson, L.J. Bond, A new technique
for the simultaneous, real-time measurement of membrane compaction and
performance during exposure to high-pressure gas, J. Membr. Sci. 171 (2000)
217.
[29] L. Brinkert, N. Abidine, P. Aptel, On the relation between compaction and
mechanical properties for ultrafiltration hollow fiber, J. Membr. Sci. 77 (1993)
123.
[30] K.W. Lawson, M.S. Hall, D.R. Lloyd, Compaction of microporous membranes
used in membrane distillation. I. Effect on gas permeability, J. Membr. Sci. 101
(1995) 99.
[31] H. Susanto, S. Franzka, M. Ulbricht, Dextran fouling of polyethersulfone ultrafil-
tration membranes—causes, extent and consequences, J. Membr. Sci. 296 (2007)
147.
[32] S.H. Wolff, A.L. Zydney, Effect of bleach on the transport characteristics of poly-
sulphone hemodialyzers, J. Membr. Sci. 243 (2004) 389.
[33] J.J. Qin, M.H. Oo, Y. Li, Development of high flux polyethersulfone hollow fiber
ultrafiltration membranes from a low a critical solution temperature dope via
hypochlorite treatment, J. Membr. Sci. 247 (2005) 137.