Journal of Membrane Science 290 (2007) 153–163

Tailoring pore size and pore size distribution of kidney dialysis

hollow fiber membranes via dual-bath coagulation approach
Qian Yang a , Tai-Shung Chung a,∗ , Y.E. Santoso b
a Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore 119260, Singapore
b Polymer Research Engineering Plastics, BASF Aktiengesellschaft, GKT/B-B1, Ludwigshafen 67056, Germany

Received 31 October 2006; received in revised form 14 December 2006; accepted 18 December 2006
Available online 4 January 2007

Abstract
Polyethersulfone (PES) hollow fiber membranes for kidney dialysis application were prepared by the dry-jet wet-spinning method. A dual-
coagulation bath technology was first time employed for fabricating the kidney dialysis membranes with a tight inner skin and loose outer
supporting layer structure. A weak coagulant isopropanol (IPA) was served as the first external coagulation bath, while water as the second bath.
Experiments demonstrate their advantages of better controlling both inner and outer skin morphology. The as-spun fibers have a higher mean
effective pore size (μp ), pure water permeation flux (PWP) and molecular weight cut-off (MWCO) with an increase in N-methyl-2-pyrrolidone
(NMP) percentage in bore fluid (i.e., internal coagulant). After being treated in 8000 ppm NaOCl solution for 1 day, fibers show larger pore sizes
and porosity in both inner and outer surfaces, and thinner inner and outer layers than their as-spun counterparts. Among them, the bleached fibers
spun with 50 wt.% NMP in bore fluid have the MWCO (43 kDa) and PWP (40 × 10−5 L m−2 Pa−1 h−1 ) suitable for kidney dialysis application.
Based on SEM observations and solute rejection performance, the further heat treated fibers in an aqueous solution is found to be an effective
way to fine tune membranes morphology and MWCO for kidney dialysis application. The solute rejection performance data of the hollow fiber
membranes spun with 55 wt.% NMP in bore fluid after heat treated at 90 ◦ C in water for 2 h were found to be very appropriate for the kidney
dialysis application.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Kidney dialysis membrane; PES hollow fiber membrane; Pore size and pore size distribution; Dual-bath coagulation; NaOCl treatment

1. Introduction
Kidney dialysis hollow fiber membranes used clinically in
the treatment of renal failure patients act to remove accumu-
lated uremic toxins, excess ions and water from the blood and to
supply those ions that are insufficient from the dialysate [1]. In
the preferred kidney dialysis process, low and middle molecular
weight uremic toxins such as uric acid, urea, creatinine, inulin
and ␤2 -microglobulin have to be removed but proteins such as
serum albumin (Mw : 67,000 Da) must be retained. The accumu-
lation of ␤2 -microglobulin (Mw : 11,800 Da) in the human body
may cause amyloidosis [2,3]. Therefore, the desirable kidney
dialysis membranes must have a suitable pore size distribution
which can remove the largest toxin molecule (␤2 -microglobulin)
while retain the smallest protein molecule (serum albumin).
∗ Corresponding author. Fax: +65 67791936.
E-mail address: chencts@nus.edu.sg (T.-S. Chung).
Usually, the blood flows in the lumen side of the fibers,
while the dialysate is counter-currently through the shell side.
Blood waste diffuses from the blood to dialysate due to con-
centration differences [4]. To reduce blood cell damage and
enhance separation performance, kidney dialysis membranes
have been designed with a thin inner selective skin to remove
toxins from the blood stream and an outer loose supporting
layer taking care of secondary separation to reduce the pas-
sage of cytokine-inducing materials from dialysate to blood
while retaining the proteins movement from blood to dialysate.
A sponge-like asymmetric structure is highly favored because
not only it may provide higher mechanical strengths but also
prevent membranes from leakage, which might happen in the
membrane structure with finger-like macrovoids after repeated
usages. In dialysis asymmetric membranes, the structures of both
the inner selective skin and the outer supporting layer influence
the diffusive permeability and selectivity [5].
The membranes used in clinical dialyzers are most
made of cellulose or synthetic polymers [6]. The usage of

0376-7388/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2006.12.036
154 Q. Yang et al. / Journal of Membrane Science 290 (2007) 153–163
polyethersulfone (PES) for kidney dialysis application has
attracted attention since 1980 due to its excellent stability
under sterilization and minimal degradation in membrane per-
formance over extended period of time [5]. However, due to
the hydrophobic nature of PES, modifications to increase its
hydrophilicity, lessen protein absorption and avoid blood clot
are needed. A combination of hydrophobic and hydrophilic
domains rather than a uniformly hydrophobic or hydrophilic
composition favors membranes higher biocompatibility. Up to
now, the most common method used for increasing PES mem-
brane hydrophilicity is by blending it with hydrophilic polymers,
such as polyvinylpyrrolidone (PVP) [3,7]. Not only is PVP a
pore former agent, but also is a water soluble polymer. Espe-
cially it has the capability to form miscible blends with PES
[8]. The addition of PVP into PES during membrane fabrica-
tion enhances solution viscosity and can potentially eliminate
macrovoids in the resultant membranes [9]. Furthermore, due
to the fact that those immiscible (i.e., unblended) PVP can be
removed mostly from the membranes [10], it minimizes the pos-
sibility of PVP leaching out during the in vivo kidney dialysis
operation.
In this work, PES kidney dialysis hollow fibers were fabri-
cated by means of a dry-jet wet-spinning technique via dual-bath
coagulation. Several authors have reported the usage of this
method in fabricating gas separation membranes [11–13]. How-
ever, to our best knowledge, the dual-bath coagulation technique
has not been employed in the study of kidney dialysis mem-
branes. Compared to the single-bath coagulation, the dual-bath
coagulation may have the advantages of better controlling both
inner and outer skin morphology. The effects of dope formu-
lation, spinning conditions and post-treatment on membrane
morphology, pore size distribution and solute rejection for kid-
ney dialysis application were systematically carried out and the
results are presented below.
2. Experimental
2.1. Materials
Polyethersulphone (Ultrason® E6020P, Ultrason is a regis-
tered trademark of BASF Aktiengesellschaft) with an average
molecular weight (Mw ) of 98,170 Da was supplied by BASF
Company, Germany. Polyvinylpyrrolidone (Merck, Singapore)
was served as an additive for hollow fiber membranes spin-
ning. N-Methyl-2-pyrrolidone (NMP) (Merck, Singapore) was
employed as the solvent, while isopropanol (IPA) (Merck, Singa-
pore) as the non-solvent. Sodium hypochlorite (NaOCl) (Acros,
Singapore) was used as the post-treatment agent to remove PVP.
Polyethylene glycol (PEG) (Aldrich, Singapore) with molecu-
lar weights varying from 600 Da to 35 kDa and polyethylene
oxide (PEO) (Aldrich, Singapore) with molecular weights from
100 to 900 kDa were utilized as the solutes to characterize pore
sizes and pore size distributions and measure the separation
performance of hollow fiber membranes. Methanol (Merck, Sin-
gapore) and n-hexane (Merck, Singapore) were used to conduct
solvent exchange in order to remove the residual solvents from
as-spun hollow fiber membranes.
2.2. Fabrication of hollow fiber membranes
To prepare the spinning dope solution, the PES (Ultrason®
E6020P) and PVP (average Mw 360,000 Da) powders were dried
at about 120 ◦ C in a vacuum oven overnight to remove the
moisture. Certain amount of dried PES was firstly dispersed
slowly into a chilled NMP according to the desired weight per-
centage and stirred continuously with a high speed mechanical
stirrer. Unless otherwise stated, PVP was then added to the poly-
mer dope solution to make its final composition constant at
16/10/74 wt.% PES/PVP/NMP. The high molecular weight PVP
is chosen because it can form a strong interaction force between
PVP and PES polymer and the entanglement effect may provide
an extraction-resistant PVP levels in membrane surface over an
extended period of time [14]. The solution was then stirred con-
tinuously at least 48 h to let it dissolve homogenously. Then, the
solution was degassed for at least 1 day before spinning. The
viscosities of the spinning solutions were measured using a cap-
illary viscometry installed in the Viscosity Measuring Units AV
360 from Schott–Geraete.
The hollow fiber membranes were prepared by the dry-jet
wet-spinning process. The spinning conditions are tabulated in
Table 1. Both dope and bore fluids were filtered by a metal filter
(pore size: 15 ␮m) before entering the spinneret to remove the
impurities. The as-spun fibers were first contacted with bore fluid
as well as air before immersed in the external coagulation bath.
Unless otherwise stated, the external coagulant used was a dual
coagulation bath which was aimed to form the membranes with
a porous outer and a dense inner surface. IPA was used as the
first coagulation bath and tap water was used as the second one.
All nascent fibers were not drawn, that is, the take-up velocity
of the hollow fiber membranes was nearly the same as the free
falling velocity in the coagulation bath.
The resultant fibers were then immersed in tap water for sev-
eral days to let the solvent exchange process occur. To facilitate
the residual solvents removal as well as to prepare samples for
the X-ray photoemission spectrometry (XPS) study, the fibers
were then immersed in fresh methanol for three times with half
an hour each and then continued with fresh hexane immersion
within the same period of time. The fibers spun at the same
dope and bore fluid compositions were separated by two groups.
One group was immersed in 8000 ppm NaOCl under stirring for
24 h to remove unblended PVP in the membrane matrix and
Table 1
Spinning conditions
Dope flow rate (ml/min) 2
Internal coagulant Various weight percentages of
NMP in de-ionized water (unless
otherwise specified)
Bore flow rate (ml/min) 1.5
Length of air gap (cm) 20
External coagulant IPA (1st), tap water (2nd) (unless
otherwise specified)
Spinneret dimensions (mm) 0.86/0.5 (o.d./i.d.)
Spinning temperature (◦ C) 26
Spinning humidity (%) 60
Take up speed (m/min) Free fall
 Q. Yang et al. / Journal of Membrane Science 290 (2007) 153–163
these membranes were coded “-aft”. The counterpart was not
NaOCl treated and coded “-bef”. Then both group fibers in their
wet conditions were then conducted freeze drying as follows:
the fibers were immersed in water for a short period before
frozen in a refrigerator overnight. Subsequently, the frozen fibers
were dried in a Thermo Savant ModulyoD freeze dryer (Thermo
electron Corp., USA). Freeze drying is a special form of dry-
ing that removes all moisture and tends to have less effect on
changing the structure and morphology of the membranes [15].
During freeze-drying, the membranes are first frozen and placed
in a strong vacuum. The water residing within the membranes
will then sublimate. Having not involved in wet surface-tension
force for the evaporation process, freeze drying thus allows the
structure of the membranes to be “locked in”.
2.3. Heat treatment of hollow fiber membranes
Hollow fiber membranes after NaOCl treatment with codes
“3-aft” and “4-aft” were kept in a glass flask with either hot
water or hot glycerol/water (50/50 wt.%) mixture at a preset
temperature with certain period of time. The bath temperature
was controlled by a Heidolph hot plate (Model: MR3001K)
with a Heidolph temperature controller (Model: EKT3001). All
fibers were heated in a stress-free condition. The fibers were
subsequently freeze dried unless otherwise specified. For those
membranes immersed in the glycerol solution, they were dried
in air at room temperature before making membrane modules.
These modules were thoroughly flushed with de-ionized water
to remove remaining glycerol before carrying out pure water
permeation flux and solution rejection performance tests.
2.4. Morphology studies of hollow fiber membranes by a
field emission scanning electron microscope (FESEM)
The freeze dried fiber samples were immersed in liquid nitro-
gen and fractured to obtain smooth cross-sections of the fibers
and then sputtered with platinum using a JEOL JFC-1300 Plat-
inum coater. The current used during the coating was 30 mA for
30 s. The cross-section, inner layer (IL), outer layer (OL), inner
surface (IS) and outer surface (OS) of the fiber samples were
observed under a JEOL JSM-6700F FESEM.
2.5. X-ray photoemission spectrometry observations of the
membranes’ inner surface
An X-ray photoemission spectrometry was used to measure
membrane’s inner surface elements (C, O, N and S). Assumed
that the solvent NMP was completely removed and membranes
matrix contains only PES and PVP, the PVP content in the inner
membrane surface can be calculated based on N and S weight
ratio:
(N (wt.%)/14) × Mw of PVP repeat unit
PVP (wt.%) =
(N (wt.%)/14) × Mw of PVP repeat unit + (S (wt.%)/32) × Mw of PES repeat unit
where Mw of a PES segment and a PVP segment shown in are
232 and 111 g/mol, respectively.
155
The analysis was carried out twice per sample and all the
measurements deviations were found to be less than 5%.
2.6. Membrane module preparation for ultrafiltration
experiments tests
Ten freeze dried fibers having a length of 25 cm were bun-
dled together. Both ends were sealed by a common epoxy
resin mixture (EP Bond A and hardener B, Hua Sen enterprise
Ltd., Taiwan). After the epoxy was thoroughly solidified, the
membrane modules were ready to mount on the setup to be
characterized in terms of pure water permeation flux (PWP)
and solute separation performance. Since the selective layer
is the inner layer, the feed was pumped into the lumen at
100 ml/min and the permeate came out from the shell side form-
ing a cross-flow filtration mode. The corresponding Reynolds
number around 25,800 indicates the feed flow was in the turbu-
lent range and the concentration polarization was less happened.
The feed concentration (PEG or PEO) was around 200 ppm to
further minimize the occurrence of concentration polarization.
Experiments were conducted at a trans-membrane pressure of
about 0.8 × 105 Pa (gauge) at room temperature. Two modules
were prepared for each hollow fiber membrane sample. The
PWP and solute rejection were taken as an average of these two
modules’ results. The measurement deviation for PWP was less
than 2% and that for solute rejection was less than 1%. Each mod-
ule was firstly subjected to the pure water permeation experiment
in order to measure the pure water permeation flux. The nor-
malized pure water permeation flux (×10−5 L m−2 Pa−1 h−1 ) is
calculated by the following equation:
Q
PWP = (2)
A · P
where Q is the permeate volume in a predetermined time period
(L h−1 ), A the effective membrane inner surface area (m2 ), and
P is the trans-membrane pressure (Pa).
Subsequent to the pure water permeation flux measurement,
the solute rejection experiment was conducted: experiments
were started by using a low molecular weight PEG and then
continued by other PEG or PEO with progressively increasing
molecular weights. Each PEG or PEO solution was circulated
for about 1 h until the whole system reached steady state, then the
permeate was collected for a predetermined period and the vol-
ume was measured before being analyzed. Two to three samples
were taken for analysis. The modules were thoroughly flushed
with deionized water between runs of different molecular weight
solutes. It was found the PWP in membrane module washing
between solute changes did not change, indicating no fouling
occurred in the tests.
The concentrations of feed and permeate were determined
by a total organic carbon analyzer (TOC) (SHIMADZU
(1)
156 Q. Yang et al. / Journal of Membrane Science 290 (2007) 153–163
ASI-5000A). The solute separation factor was calculated by
using the following equation:
 
Cp
R= 1− × 100 (3)
Cf
where Cp and Cf are the solute concentration in the permeate
and in the feed solution, respectively.
The solute rejection data were further used to estimate the
mean pore size and the pore size distribution of the selective
layer of the hollow fiber membranes.
2.7. Characterization of the pore size and pore size
distribution of hollow fiber membranes by solute transport
Based on their mean pore size, membranes for kidney dialysis
application can be categorized as either nanofiltration or ultra-
filtration membranes. Ultrafiltration membranes have pore size
in the range of 10–100 nm, while nanofiltration is in the range
of 1–10 nm [16]. Therefore, these membranes can be charac-
terized by the pore size and the pore size distribution obtained
from solute rejection performed via ultrafiltration experiments.
This method provides a very simple technique for indicating
the performance of a given membrane. For this reason, it is fre-
quently used for the industrial assessment of membranes and
many researchers have reported this method for characterizing
ultrafiltration and nanofiltration membranes [3,17–20].
The Stokes radii of the solutes were calculated based on
average molecular weights [21,22].
For PEG r = 16.73 × 10−12 × M 0.557
For PEO r = 10.44 × 10−12 × M 0.587
where r is the Stokes radius of the solute (m) and M is the
molecular weight (kg/mol)
Michaels [23] showed that solute rejection can be expressed
by a log-normal probability function of solute size, for both bio-
logical and synthetic membranes, as expressed in the following
equation:
 y
1 ln ds − ln μs
e−u /2 du, where y =
2
R = erf(y) = √
2π −∞ ln σg
(6)
Fig. 1. Cross-section of fibers spun via a single coagulation bath using water as bore fluid and external coagulant. (A) PES/NMP (18/82 wt.%), viscosity: 1.450 Pa s.
(B) PES/PVP/NMP (18/5/77 wt.%), viscosity: 14.926 Pa s. (C) PES/PVP/NMP (18/10/72 wt.%), viscosity: 67.703 Pa s.
where R is the solute separation factor (%), ds the solute diame-
ter, μs the geometric mean diameter of solute at R = 50%, σ g is
the geometric standard deviation about μs , defined as the ratio of
ds at R = 84.13% and R = 50%. When the solute separation factor
R (%) of an ultrafiltration membrane is plotted versus the solute
diameter on a log-normal probability coordinate, a straight line
is obtained as:
F (R) = A + B (ln ds ) (7)
By ignoring the steric and hydrodynamic hindrance effects
of the pore on solutes, the mean effective pore size, μp , and the
geometric standard deviation, σ p , can be considered the same
as the μs and σ g . Therefore, based on μp and σ p , the pore size
distribution of a UF membrane can be expressed as the following
probability density function by taking the derivative form of Eq.
(6) with respect to R:
 
dR(dp ) 1 (ln dp − ln μp )2
= √ exp − (8)
ddp dp ln σp 2π 2(ln σp )2
Furthermore, the molecular weight cut-off (MWCO) of the
membranes, defined as molecular weight of solutes where the
rejection of membranes reaches 90%, can be determined from
the plot of Eq. (7).
3. Results and discussion
3.1. The optimizations of spinning conditions to fabricate
hollow fiber membranes with morphology suitable for
kidney dialysis application
(4)
(5) Normally the exchanges of the internal and external coagu-
lants with the dope solvent through the nascent fiber surfaces
results in different precipitation fronts and creates different
membrane morphology. In some spinning conditions, when the
dope solution (PES/NMP 18/82%) comes in contact with tap
water serving both as the internal (bore fluid) and external coag-
ulants, polymer precipitation takes place at the two fiber surfaces
after leaving the spinneret. The fiber inner and outer surface
structures are fixed very rapidly due to the instantaneous poly-
mer precipitation, causing the final three-layer structure after
the dope solvent is leaching out (Fig. 1A). In addition, the
speeds of precipitation fronts from both inner and outer surfaces
 Q. Yang et al. / Journal of Membrane Science 290 (2007) 153–163 157

Fig. 2. SEM images of fibers spun from PES/PVP/NMP (18/10/72 wt.%) dope via a single coagulation bath using water as bore fluid and external coagulant (A)
before NaOCl treatment; (B) after NaOCl treatment; IL: inner layer; OL-outer layer; IS: inner surface; OS: outer surface.

toward the membrane center are comparable (strictly speak-
ing, the inner one may be slightly faster than the outer one
because the inner surface came into contact with the internal
coagulant earlier than the outer surface). This creates almost
symmetric finger-like macrovoids (but slightly toward the outer
skin) along the membrane middle. Both the external and inter-
nal cross-sections contain fingerlike macrovoids, whereas the
central is full of big macrovoids. This is due to the fact that the
fiber inner and outer surface structures and dimensions are fixed
very rapidly due to instantaneous polymer precipitation, caus-
ing the formation of middle macrovoids after the dope solvent is
leaching out.
The macrovoid formation mechanisms have been a big sub-
ject debated among membrane scientist. It is widely accepted
that the ends of macrovoid are prone to defect-happening due
to their weak mechanical strength. One of the effective ways to
suppress the formation of finger-like macrovoids is by increas-
ing the dope viscosity [24] or by adding surfactants [25] or a high
viscosity component [9]. The addition of PVP has increased the
dope viscosity as observed in our experiments as well as reported
by other research groups [8,26,27].
Fig. 1 shows the membrane cross-section morphology as a
function of spinning dope viscosity. The dope viscosity increases
from 1.450 to 14.926 and 67.703 Pa s when the dope contains
5 and 10 wt.% PVP, respectively. Fig. 1B shows that the addi-
tion of 5 wt.% PVP is not enough to eliminate the macrovoid
structure completely. Nevertheless, the finger-like macrovoid
structure moves inward and the two edges of hollow fiber mem-
brane are free of macrovoids. A further increase in PVP amount
to 10 wt.% results in the complete disappearance of finger-like
macrovoid structure as shown in Fig. 1C. This is attributed to a
tremendous increase in spinning dope viscosity. With such a high
viscosity, the intrusion of both internal and external coagulant
(water) during the phase inversion is hindered.

Fig. 3. SEM images of the fibers spun via dual coagulation bath: IPA (1st) + H2 O (2nd) (A) before NaOCl treatment; (B) after NaOCl treatment (dope: PES/PVP/NMP
(16/10/74 wt.%); bore fluid: NMP/H2 O (40/60 wt.%)).
158 Q. Yang et al. / Journal of Membrane Science 290 (2007) 153–163

Fig. 4. SEM images of the fibers spun via dual coagulation bath with a bore fluid of 50/50 NMP/H2 O (A) before NaOCl treatment; (B) after NaOCl treatment; scale
bar: 100 nm.

In fact, the presence of PVP in the dope solution not only pro-
motes the formation of sponge-like structure but also influences
the surface chemistry of pores (which will be discussed later).
During the pore formation, the PVP is preferentially located in
the pore surface [28] because PVP likes contacting with water.
This leads to the reduction of pore size or even pore blocking.
One of the easy and effective ways to remove the PVP is by
using sodium hypochlorite [29] because the membrane forming
material (i.e., PES) is fairly resistant to the hypochlorite solu-
tion [10,29]. Compared the membrane morphology before and
after NaOCl treatment (Fig. 2), the pores can be visibly seen
in the inner and outer surface after NaOCl treatment which is
attributed to the removal of PVP surrounding the pores.
However, when using water as the internal and external coag-
ulants, an undesirable membrane structure for kidney dialysis
application is formed with thick dense skins at both the inner
and outer membrane layer even after the fibers are treated with
NaOCl. This structure generates a significant mass transfer resis-
tance during the kidney dialysis process. The formation of dense
skin layers is mainly due to the fact that water is a powerful
coagulant which induces rapid coalescence of polymer chains.
Thus, it is expected that by utilizing a mixture of solvent and
non-solvent as bore fluid would delay the demixing process and
retard the dense layer formation.
Besides a thin selective inner surface, kidney dialysis mem-
branes prefer a porous outer surface to reduce the overall
transport resistance of the solutes. Utilizing a dual coagulation
bath with different coagulant strengths appears to be a promising
approach to fabricate kidney dialysis hollow fiber membranes
with a desirable porous outer surface. This is due to the fact that
the chemistry of both coagulant baths can be tailored in order to
achieve the desired morphology. A low strength coagulant in the
first coagulation bath may result in a porous outer surface, while
a high strength bore fluid may produce a tight inner skin. Water
is used in the second coagulation not only to lower the cost but to
fully precipitate and stabilize the nascent membrane structure.

Fig. 5. SEM images of the fibers spun via dual coagulation bath with a bore fluid of 55/45 NMP/H2 O (A) before NaOCl treatment; (B) after NaOCl treatment; scale
bar: 100 nm.
 Q. Yang et al. / Journal of Membrane Science 290 (2007) 153–163 159

Fig. 6. SEM images of the fibers spun via dual coagulation bath with a bore fluid of 60/40 NMP/H2 O (A) before NaOCl treatment; (B) after NaOCl treatment; scale
bar: 100 nm.

3.2. The influence of bore fluid compositions and dual
coagulation bath on the morphology and solute rejection
performance of hollow fiber membranes
Table 1 summarizes the spinning conditions. Isopropanol
is used in the first coagulation bath, while 16/10/74 wt.%
PES/PVP/NMP is the spinning dope composition. Various
NMP/water mixtures are employed as bore fluids. IPA and NMP
were chosen because both are biological and environmental
friendly solvents. Fig. 3 illustrates the membrane morphology
when 40/60 wt.% NMP/H2 O was used as bore fluid. It can be
seen that the desirable porous outer surface has been successfully
created but with rather thick dense layers in two edges.
With NMP/H2 O as the bore fluid, the hydrophilic PVP dif-
fuses towards to the interface between the nascent fiber and the
bore fluid during the spinning process. The addition of NMP
in bore fluid delays the demixing, which makes the nascent
inner surface softer and thus more PVP diffuses toward the inner
membrane surface than stays in the bulk during the membrane
forming process. This phenomenon is confirmed by XPS results
as shown in Table 3 where a higher PVP content was found in the
inner surface (51.56%) than the theoretical PVP content in the
dope (38.46%). From FESEM observations (Ref. to Figs. 3–6),
an increase in NMP in bore fluid results in a decrease in dense
inner layer thicknesses. This is understandable as the presence
of more NMP in bore fluid helps delay the demixing. As a result,
the pure water permeation flux of the as-spun fibers increases
with an increase in NMP percentage in bore fluid as shown in
Table 2.
Log-normal probability plots of solute separation versus
solute diameter both before and after NaOCl treatment are shown
in Fig. 7. The mean effective pore size (μp ) and the geometric
standard deviation (σ p ) are obtained according to the method
described in Section 2.7. The Stokes diameter of the solute that
achieves 90% separation can be obtained from Fig. 7 and the
corresponding molecular weight cut-off can be back-calculated
from Eq. (4). The resultant σ p , μp and MWCO are all given in
Table 2. The cumulative pore size distributions and the prob-
ability density function curves of the hollow fiber membranes
are given in Fig. 8. From Table 2 and Fig. 8, it is obvious that
the as-spun fibers’ μp and MWCO are increased with increasing
NMP in bore fluid. The pore size distribution becomes broader
after the NaOCl treatment.
Apparently, the FESEM images show that the fibers after
NaOCl treatment have larger pore sizes and more porous struc-
ture in the inner surface. This is because the space originally
occupied by PVP becomes pores after PVP leaching out from
the membrane matrix. The removal of PVP entrapped in the

Table 2
Mean effective pore size (μp ), geometric standard deviation (σ p ), pure water permeation flux (PWP) and molecular weight cut-off (MWCO) of the hollow fiber
membranes spun with 16/10/74 wt.% PES/PVP/NMP as the dope and with different bore fluid compositions
ID Bore fluid Before NaOCl After NaOCl

NMP/H2 O μp (nm) σp PWP MWCO (Da) μp (nm) σp PWP MWCO (Da)

(wt.%) (×10−5 L m−2 Pa−1 h−1 ) (×10−5 L m−2 Pa−1 h−1 )

1 40/60 1.76 1.84 3.56 4966 1.97 1.49 10.88 3,821

2 50/50 2.34 1.47 3.89 5013 3.47 2.17 40.03 42,643
3 55/45 2.86 1.58 5.43 8421 6.04 3.60 45.63 214,027
4 60/40 2.91 1.57 7.23 8569 17.96 2.97 334.04 1,350,525
160 Q. Yang et al. / Journal of Membrane Science 290 (2007) 153–163

Fig. 7. Solute separation curves plotted on a log-normal probability coordinate system of hollow fiber membranes (A) before NaOCl treatment; (B) after NaOCl
treatment. IDs 1, 2, 3 and 4 for correspondingly 40/60, 50/50, 55/45 and 60/40 NMP/H2 O used as the bore fluids.

Fig. 8. (A and B) Cumulative pore size distribution curves; (C and D) probability density function curves of hollow fiber membranes. IDs 1, 2, 3 and 4 for
correspondingly 40/60, 50/50, 55/45 and 60/40 NMP/H2 O used as the bore fluids.

inner surface can be further confirmed by XPS results. Table 3

shows that the PVP amounts in the membrane inner surface
are all decreased after NaOCl treatment. In addition, the higher Table 3
PVP amount in the hollow fiber membrane’s inner surface determined by XPS
NMP in bore fluid, the more PVP percentage are removed. This
analysis
is consistent with the previous hypothesis that a high NMP con-
tent in bore fluid results in a loose inner skin, leading to the easy Fiber ID 1 2 3 4
removal of PVP during the NaOCl treatment. Before NaOCl 51.56 wt.% 40.40 wt.% 48.04 wt.% 64.07 wt.%
Correlating the FESEM images with the solute rejection per- After NaOCl 36.75 wt.% 27.31 wt.% 30.38 wt.% 39.24 wt.%
formances, we find that a larger pore size in the inner membrane Decrease ratio 28.7% 32.4% 36.8% 38.8%
surface provides a larger μp and a higher MWCO. Therefore, IDs 1, 2, 3 and 4 for correspondingly 40/60, 50/50, 55/45 and 60/40 NMP/H2 O
the fiber after NaOCl treatment may show increases in μp and used as the bore fluids.
 Q. Yang et al. / Journal of Membrane Science 290 (2007) 153–163 161

Fig. 9. SEM images of “3-aft” fibers after heated in (A) 60 ◦ C; (B) 75 ◦ C; (C) 90 ◦ C water for 2 h.

MWCO. This is especially true for those fibers spun with a bore
fluid containing a high NMP percentage. For example, the mean
effective pore sizes of as-spun fibers are in the range of 1–3 nm
but they increase to 6.04 and 17.96 nm after NaOCl treatment if
the bore fluid contains 55 and 60 wt.% NMP, respectively. The
MWCO of as-spun membranes is less than 10,000 Da but the
MWCO of bleached fibers increases to 43, 214 and 1350 kDa
if the bore fluid contains 50, 55 and 60 wt.% NMP, respec-
tively. Among them, the fiber with a MWCO of 42,643 Da,
sitting between the lowest molecular weight (12 kDa) of the
toxic molecules to be removed and the highest molecular weight
(67 kDa) of the proteins to be retained. In addition, its PWP
(4.0 × 10−4 L m−2 Pa−1 h−1 ) is reasonably high for the kidney
dialysis application [3].
3.3. The influence of heat treatment on fiber morphology
and solute rejection performance
Several researchers [3,20] reported the influence of various
heat treatment conditions on the PES UF membrane perfor-
mance. Heat-treated PES UF fibers in the air shrank as evidenced
by a decrease in flux and an increase in solute separation. How-

Fig. 10. (A) Cumulative pore size distribution curves and (B) probability density function curves of “3-aft” hollow fiber membranes heated in water bath at different
temperature for 2 h.
162 Q. Yang et al. / Journal of Membrane Science 290 (2007) 153–163
Table 4
Summary of the μp , σ p , PWP, MWCO and remaining PVP in the inner surface of the “3-aft” hollow fiber membranes heat treated in water at different temperatures
for 2 h
Mem. ID μp (nm) σp
3-aft 6.04 3.60
Water-60 ◦ C-2 h 3.38 4.19
Water-75 ◦ C-2 h 5.23 2.61
Water-90 ◦ C-2 h 5.51 2.34
ever, water flux increased while MWCO remained the same
when the heat treatment was conducted in hot water at 95 ◦ C
for 30 min. Clearly, heat treatment can change the morphol-
ogy, especially the surface morphology, which will affect their
performance.
Since fibers spun with 55 wt.% NMP in bore fluid and then
treated with NaOCl (code: “3-aft”) have a much larger MWCO
(214 kDa) than the desirable one for kidney dialysis membranes,
these fibers (referred as “3-aft”) were used in the heat treatment
study to tailor their structure suitable for the kidney dialysis
application. The study was carried out to investigate the effect
of water temperature for heat treatment on membrane morphol-
ogy and performance while keeping the heat treatment period
to 2 h. Fig. 9 shows the cross-section, inner and outer surface
morphology. Some pores in the inner surface seem to somewhat
collapse or get closer. This leads to the MWCO decline with an
increase in water treatment temperature (ref. to Fig. 10). Table 4
summarizes a comparison of the effect of varying water treat-
ment temperature on membrane pore size, PWP and MWCO.
The “3-aft” fibers after treated in 90 ◦ C water for 2 h have a
satisfactory MWCO of around 67 kDa and a reasonable high
PWP of 4.0 × 10−4 L m−2 Pa−1 h−1 suitable for kidney dialysis
application. This fiber has a high PWP and proper MWCO due
to the fact that the 90 ◦ C water treatment cannot only remove
more PVP but also shrink pore size simultaneously as shown in
Table 4, and the former factor results in a more permeable inner
layer as shown in Fig. 9.
4. Conclusions
The influences of spinning dope compositions, both internal
and external coagulant compositions and post-treatment con-
ditions on PES kidney dialysis membrane’s morphology, pure
water permeation flux, and solute rejection performance were
systematically investigated. The following conclusions can be
drawn from this experimental work:
(1) The finger-like macrovoids in PES hollow fiber membranes
can be suppressed by adding 10% PVP (Mw of 360 kDa) into
the spinning dope solution as the result of a drastic increase
in dope viscosity.
(2) A novel IPA/water dual-coagulation bath is found to be an
effective way to control both inner and outer skin morphol-
ogy. Membranes with a thin selective inner skin and a loose
outer supporting layer have been fabricated by this method
for kidney dialysis application.
PWP (×10−5 L m−2 Pa−1 h−1 MWCO (Da) PVP in IS (%)
(L m−2 bar−1 h−1 ))
45.63 214,027 30.38
25.51 108,288 23.13
29.26 79,432 24.02
40.01 66,946 18.60
(3) After being treated in 8000 ppm NaOCl solution for 24 h,
fibers usually show larger pore size and porosity in both
inner and outer surface and thinner inner and outer layer.
As the result these fibers show much larger μp , PWP
and MWCO than as-spun counterparts. The solute sep-
aration data reveal that the bleached fibers spun with
50 wt.% NMP have the MWCO of 43 kDa and PWP
of 4.0 × 10−4 L m−2 Pa−1 h−1 suitable for kidney dialysis
application.
(4) Heat treatment in a hot aqueous solution is an effective way
to fine tune membrane pore size, porosity and MWCO. Hol-
low fiber membranes spun with 55 wt.% NMP in bore fluid
and heat treated in 90 ◦ C water for 2 h were found to be very
appropriate for kidney dialysis application with MWCO of
around 67 kDa.
Acknowledgements
The authors would like to thank BASF Company, Germany
for funding this research project with a grant number of R-279-
000-188-592. The authors are indebted to Dr. Martin Weber and
Prof. Volker Warzelhan both from BASF, Germany for their
invaluable technical suggestions and support throughout this
work. We are also highly appreciated Dr. Wang K.Y. for his
help on the system design.
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