Journal of Membrane Science 218 (2003) 173–183

Cellulose acetate hollow fiber ultrafiltration membranes

made from CA/PVP 360 K/NMP/water
Jian-Jun Qin a,∗ , Ying Li b , Leng-Siang Lee c , Hsiaowan Lee a
aCentre for Advanced Water Technology, Singapore Utilities International Pte Ltd., Blk 2, #241,
Innovation Centre (NTU), 18 Nanyang Drive, Singapore 637723, Singapore
b Institute of Environmental Science and Engineering, Blk 2, #237, Innovation Centre (NTU),

18 Nanyang Drive, Singapore 637723, Singapore

c Department of Civil Engineering, National University of Singapore, 10 Kent Ridge Crescent, Singapore 119260, Singapore
Received 1 March 2003; accepted 4 April 2003

Abstract
Hydrophilic hollow fiber ultrafiltration (UF) membranes have been prepared from a new dope solution containing cellulose
acetate (CA)/poly(vinyl pyrrolidone) (PVP 360 K)/N-methyl-2-pyrrolidone (NMP)/water with a mass ratio of 19.0/5.0/74.8/1.2
by using a dry-jet wet spinning process. The effect of air-gap length was studied. The as-spun fibers were post-treated by
means of a hypochlorite solution of 200 mg l−1 (200 ppm) over different duration. The morphology of the membranes was in-
vestigated by Scanning Electron Microscopy (SEM). Pure water fluxes and solute retentions of the membranes were measured
and different fouling resistances were analyzed. The experimental results showed that water flux of a membrane decreased
while retention increased with increasing air gap. Fluxes of hypochlorite treated membranes were three times higher than
that of an untreated membrane and retentions of the treated membranes were much lower. A 6 h treatment with 200 mg l−1
hypochlorite solution could achieve a CA UF membrane with a high pure water flux of 220 × 10−5 l m−2 h−1 Pa−1 . SEM
images revealed that, PVP additive would favor the suppression of macrovoids and the thickness of inner skin increased with
increasing air gap. PVP contents in the blend membrane could be significantly removed with the hypochlorite treatment. As
a result, the treated CA membrane experienced higher fouling tendency than the untreated membrane. It was concluded that
hypochlorite treatment altered the pore size of hollow fiber UF membranes made from the blend of CA and PVP 360 K. This
is an extended conclusion to the published results and an attempt at explaining some differences were provided.
© 2003 Elsevier Science B.V. All rights reserved.
Keywords: Cellulose acetate; Poly(vinyl pyrrolidone); Hollow fiber spinning; Hydrophilic ultrafiltration membranes; Hypochlorite treatment

1. Introduction tration (MF) and gas separation [2–4]. CA membranes

The cellulose acetate (CA) membrane was the first
high performance asymmetric membrane [1]. It has
been widely used for reverse osmosis (RO), microfil-
∗ Corresponding author. Tel.: +65-67941507;
fax: +65-67942791.
E-mail address: jjqin@cawt.sui.com.sg (J.-J. Qin).
have excellent hydrophilicity that is very important in
minimizing fouling, good resistance to chlorine and
solvent [5–7]. A regenerated CA membrane that was
hydrolyzed from cellulose acetate has significantly
improved solvent-resistance and thermostability [8].
Commercial CA membranes are either flat sheet or
spiral-wound modules [2,3]. The hollow fiber con-
figuration has become a favorite choice because the

0376-7388/03/$ – see front matter © 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0376-7388(03)00170-4
174 J.-J. Qin et al. / Journal of Membrane Science 218 (2003) 173–183
hollow fiber membrane has three major advantages:
(1) hollow fiber modules have much larger ratio of
membrane area to unit volume (several thousand
M2 /M3 ) compared to flat and spiral-wound modules
(a few hundred M2 /M3 ), and hence higher productiv-
ity per unit volume of membrane module; (2) they are
self-supporting which can be back-washed to recover
the flux; and (3) they have good flexibility in the mode
of operation. Hao and coworkers [9,10] have studied
CA hollow fiber membrane preparation by the dry-jet
wet spinning for gas separation and for ultra low pres-
sure RO application. There are a number of patents
on the fabrication of CA hollow fiber MF mem-
branes [11–13]. An activated carbon-filled cellulose
acetate hollow fiber membrane for cell immobiliza-
tion and phenol degradation has been studied recently
[14].
The air-gap length during spinning affects the per-
formance of final fibers and this has been studied by
a number of researchers [15–19]. Chung and Hu [15]
reported that an increase in air-gap distance resulted in
a significant decrease in permeation of the membrane,
most likely due to a higher gravity-induced elonga-
tional stress on the fibers spun from a higher air-gap
distance, resulting in a greater orientation and tighter
molecular packing. Porter [17] stated that an increase
in the air-gap length would result in tighter fibers with
lower permeability and increased retentivity because
of an increase in the degree of orientation due to the
added weight of the fiber below and the extended
polymer chains. Liu et al. [18] demonstrated that the
average size of pores on the inner surface of polysul-
fone/polyethersulfone membranes decreased when the
air-gap length increased due to the nascent fiber being
stretched and elongated by its own weight, resulting
in the polymer aggregates moving closer together and
rearranging themselves into a state of greater stability.
However, very few studies on CA hollow fiber ultra-
filtration (UF) membranes have been published.
PVP as an additive is often blended into the dope
solution to increase hydrophilicity and flux of mem-
branes [19–23]. However, the addition of PVP with
high molecular mass results in a low flux membrane
due to swelling of the residual PVP at the surface of
pore walls when water passes through the membrane
pores [19,21]. Therefore, hypochlorite treatment has
been applied to increase flux of MF/UF membranes
made from a blend of PVP and hydrophobic poly-
mers [21–25]. Wienk et al. [22] investigated the ef-
fect of hypochlorite treatment on a hollow fiber UF
membrane made from a blend of PES and PVP 360 K
and concluded that hypochlorite treatment reduced the
swelling of PVP in the pores of the membranes without
substantially changing the pore structure. Recently, Xu
et al. [23] studied the effect of hypochlorite treatment
on PEI/PVP hollow fiber UF membranes for oil/water
separation. They reported that the treated membranes
showed an obvious lower solute retention or larger
pores than that of untreated membranes. They also
found that the addition of PVP with high molecular
mass would suppress the formation of macrovoids.
More recently, the authors [24,25] have reported an
optimum treatment time with hypochlorite and an op-
timum hypochlorite concentration to achieve high flux
membranes spun from a blend of polysulfone and PVP.
To our best knowledge, it does not appear to report
how hypochlorite treatment impacts on a hollow fiber
UF membrane fabricated from blends of CA and PVP
of high molecular mass.
This paper explores the effects of air-gap length
and hypochlorite treatment on properties and mor-
phology of CA hollow fiber UF membranes pre-
pared from a new dope solution containing CA/PVP
360 K/NMP/water.
2. Experimental
2.1. Materials
The membrane material, cellulose acetate (CA-
398-30) with acetyl content of 39.7 wt.% was pur-
chased from Eastman Chemical Company (Kingsport,
USA). Poly(vinyl pyrrolidone) (PVP 360 K, average
MW 360,000) polymer was supplied by Sigma. The
solvent, N-methyl-2-pyrrolidone (NMP, >99%) was
supplied by Merck (Darmstadt, Germany). Poly(vinyl
pyrrolidone) [PVP 10 K (average MW 10,000) and
PVP 24 K (average MW 24,000)] from Sigma–Aldrich
and bovine serum albumin (BSA, MW 66,000) from
Calbiochem® Biosciences, Inc. (La Jolla, CA, USA)
were used to characterize the separation performance
of the hollow fiber UF membranes. Sodium hypochlo-
rite solution (10–12%) from SINO Chemical Co.
(Singapore) was used in the post-treatment of the UF
hollow fiber membranes.
 J.-J. Qin et al. / Journal of Membrane Science 218 (2003) 173–183
2.2. Fabrication of hollow fiber UF CA membranes
2.2.1. Preparation of a spinning dope
CA and PVP 360 K were dried in an oven at 65 ◦ C
to remove the moisture in the respective polymer sam-
ples. The weight loss of the polymers was monitored
for 11 days until constant weight was achieved. The
amount of water content in both CA and PVP 360 K
could be determined from the final weight loss and
was used to design the formulation of a spinning dope
containing water.
The spinning dope of CA/PVP 360 K/NMP/water
was prepared by the following procedure. First, the
solvent, NMP and the additive, undried PVP 360 K
were well mixed in a glass bottle. The undried mem-
brane polymer CA was then added into the mixture
with the amount of water in the undried CA and PVP
taken into consideration. After that, the mixture was
stirred for at least 48 h to ensure the dope was a true
solution, which was supported by the observation that
the dope was still transparent after a period of 3-month
storage in a 50 ml triangle flask. Finally, the formu-
lated dope in a solution tank and the bore fluid in a
metal canister were degassed to remove any gas bub-
bles before spinning.
2.2.2. Spinning of hollow fibers
Hollow fiber UF membranes were spun using the
well-known dry-jet wet spinning process [15,25,26].
The dope solution and the bore fluid were fed into the
spinneret by means of pressure from a nitrogen gas
cylinder. The flow rates of the dope solution and the
bore fluid could be regulated using valves that were
provided. A flow meter was attached to the bore fluid
setup to measure the flow rate.
P
2.3. Post-treatment of hollow fiber UF membranes
The as-spun fibers were rinsed in flowing town wa-
ter at room temperature for 16 h. After rinsing, the
fibers were immersed in a 50% aqueous glycerol solu-
the effective
tion for 48 h and then dried in air at room temperature
before used for making test modules. The pure water
fluxes and solute retentions of the modules were then
measured.
To investigate the effect of hypochlorite treatment
on membrane properties, the rinsed fibers were im-
mersed in a hypochlorite solution of 200 mg l−1 over
175
different periods of time up to 48 h. Before the treat-
ment, pH of the hypochlorite solution had to be ad-
justed from 11.4 to 7.0 by using H2 SO4 as CA mem-
branes could not tolerate high pH. The treated fibers
were then rinsed again in flowing town water. After
that, the same procedure as described above was fol-
lowed to characterize the treated fibers.
2.4. Characterization of hollow fiber UF
membranes
2.4.1. Measurements of flux and retention
The experiments to measure flux and retention of
hollow fiber UF membranes were carried out at tem-
perature 25 ± 0.5 ◦ C in a cross-flow filtration setup as
shown in Fig. 1. Six fibers with the length of around
30 cm were assembled into a test module. Since the
hollow fibers had an inner dense skin, the feed was
pumped into the lumen side of the fibers. The permeate
was then collected at the bottom of the U type modules.
In the tests, ultra pure water was first used to charac-
terize the pure water flux of a fresh membrane. Feed
solutions containing 100 mg l−1 of different solutes in
ultra pure water were then used to test the separation
performance of the membrane. After that, the fouled
membrane was flushed with ultra pure water and the
pure water flux of the fouled membrane was mea-
sured again. The average transmembrane pressure was
around 100 kPa and the feed flow rate was adjusted to
allow a feed velocity of 1 m s−1 . The solute concen-
tration in the feed or in the permeate was determined
by a TOC-5000A Analyser (Shimadzu). The perme-
ate flux for an inner skin membrane was calculated by
Eq. (1). The retention was calculated by Eq. (2).
Q Q
Flux = = (1)
A P Nπdi
where Q is the volume flow rate of permeate (l h−1 ),
A the effective membrane area (m2 ), P the trans-
membrane pressure (Pa), N the number of fibers, di
the inner diameter of fiber (m), and
length of fiber (m).


Cp
Retention = 1 − × 100% (2)
Cf
in which, Cf (mg l−1 ) and Cp (mg l−1 ) represent the
solute concentrations in the feed and permeate, respec-
tively.
176 J.-J. Qin et al. / Journal of Membrane Science 218 (2003) 173–183

Fig. 1. Experimental setup in testing of hollow fiber UF membranes.

2.4.2. Study of fouling tendency of hollow fiber P

Jva = (5)
membranes µ(Rm + Ra )
A UF membrane would show a reduction in flux where P is the transmembrane pressure, Rm the hy-
with fouling. One of the most significant flux reduc- draulic membrane resistance, µ the viscosity of the
tion mechanisms is concentration–polarization at the solution, Ra the hydraulic resistance of the adsorbed
membrane surface. This phenomenon would lead to layer and σ Π the osmotic pressure.
an increase in the osmotic pressure. Membrane foul- For comparison, the normalization of fluxes and
ing due to adsorption of solute molecules on the mem- flux reductions are usually computed with respect to
brane surface and in the membrane pores would then the individual membrane resistances of the individual
occur. membrane. The relative flux (Jr ) is obtained by nor-
The osmotic pressure-adsorption model [27] was malizing Jv by Jvw and represented as Eq. (6):
used in this study. Under normal operating conditions,
the flux would decrease due to two main mechanisms: 1 − Π
Jr = (6)
(i) reduction in hydrodynamic driving force by os- 1 + Ra
motic pressure (σ Π) and (ii) increase in fouling re- where the normalized resistance parameters are
sistance (Ra ) from surface adsorption and pore plug-
Ra σ Π
ging. Ra = and Π =
The pure water flux through a fresh membrane (Jvw ) Rm P
can be described by Darcy’s law (3). The solution flux Thus, the total flux reduction (Jrt ) can be represented
(Jv ) and pure water flux through a fouled membrane as
(Jva ) can be represented as in Eqs. (4) and (5).
Π  + Ra
Jrt = 1 − Jr = (7)
P 1 + Ra
Jvw = (3)
µRm In the case where no fouling occurs, then Jrt = 0. This
implies that no flux reduction relative to pure water is
P − σ Π observed. As Jrt → 1, the flux reduction is very large
Jv = (4)
µ(Rm + Ra ) and it would mean that serious fouling has occurred.
 J.-J. Qin et al. / Journal of Membrane Science 218 (2003) 173–183 177

2.4.3. Morphology study by SEM

For Scanning Electron Microscopy (SEM) study,
the as-spun fiber samples were immersed in liquid ni-
trogen and fractured to obtain tidy cross-section of
fibers, followed by an ethanol–hexane–air drying pro-
cedure [28]. The fibers were then dried in a vacuum
oven for at least 3 h at room temperature. Following
which, they were immediately sputtered with gold us-
ing JEOL® JEE-400 Ion Sputtering Device. To inves-
tigate the structure and morphology of the fibers, these
samples were studied using a JEOL® JSM 5310 LV
scanning microscope.
Fig. 2. Weight loss of polymers vs. drying time.

3. Results and discussion 3.2. Morphology of hollow fiber membranes

3.1. Formulation design of a spinning dope 3.2.1. Effect of air gap

containing water Figs. 3 and 4 show SEM images of hollow fiber
membranes spun from an air gap of 550 and 880 mm,
CA and PVP 360 K polymers at room temperature respectively. The fiber diameters measured from the
absorb moisture due to their hydrophilic properties. SEM images are shown in Table 2. It can be seen
Normally, the moisture has to be removed before that the outer diameter or wall thickness of a fiber
making a spinning dope. The step to remove moisture decreased with increasing air gap due to the enhanced
may be omitted if the dope is purposely designed elongation of a nascent fiber in an increased air gap
to contain water and the moisture contents in the while the inner diameter remained the same.
polymers remain constant in the environment of al- Figs. 3a and b and 4a and b show that the
most unchanged temperature and humidity, which is cross-sections of the as-spun fibers regardless the air
the case in this study. Two advantages are apparent. gap had sponge-like structures. The observed mor-
One is savings on process time and energy (normally phology confirmed that addition of high MW PVP
the moisture is removed by heating). Another is the in the spinning dope would favor the suppression of
ease in mixing polymers with the non-solvent water macrovoids [21,23,25]. Figs. 3c and 4c indicate that
and the solvent. However, the quantity of the mois-
ture contents in CA and PVP 360 K polymers have Table 1
to be determined before designing the dope formu- Experimental parameters used in spinning of CA hollow fiber UF
lation. membranes
Fig. 2 shows the loss in weight of the polymers Parameters Range of variables
over time during heating. The weight loss could be
Dope solution composition CA/NMP/PVP 360 K/water
attributed to the removal of moisture. It could be (19/74.8/5/1.2)
observed that weight loss of the polymers would Dope flow rate (g min−1 ) 0.29
tend to stabilize after the 8th day. The moisture con- Bore fluid composition Water
tent of CA and PVP 360 K was found to be 5.51 Bore fluid temperature (◦ C) 24
and 2.22%, respectively. As a consequence, 60.60 g Bore fluid flow rate (cm3 min−1 ) 0.85
Air-gap distance (mm) 550 or 880
CA, 225 g NMP and 15.30 g PVP 360 K could be Take-up speed (m min−1 ) 0.71
mixed in practice to obtain a designed dope formu- Coagulant temperature (◦ C) 30
lation of CA/NMP/PVP 360 K/water in a ratio of External coagulant Water
19.0/74.8/5.0/1.2. Experimental parameters used in the Dimensions of spinneret (mm) 1.0/0.6 (o.d./i.d.)
spinning of hollow fiber membrane are summarized in Spinneret temperature (◦ C) 24
Room relative humidity (%) 60–62
Table 1.
178 J.-J. Qin et al. / Journal of Membrane Science 218 (2003) 173–183

Fig. 3. SEM images of CA hollow fiber membrane spun from an air gap of 550 mm. (a) Overall, magnification: 75×; (b) partial cross-section,
magnification: 1000×; (c) inner edge, magnification: 5000×; (d) outer edge, magnification: 10,000×.

the inner edges of the fibers were dense but Fig. 3d
(where the outer layer faces the top-right) and Fig. 4d
show that the outer edges were fully microporous,
which suggested that the hollow fiber membranes had
an inner dense skin. The as-spun fibers with an inner
dense skin and outer porous surface were formed
due to the fact that an instantaneous phase separation
started from the inner surface of the nascent fiber
immediately after the spinning dope exited from the
spinneret and the demixing of the dope solution con-
tinued toward to the outer surface as the fiber fell
through an air gap of 550 or 880 mm, finally the
whole membrane structure was completed by the in-
ner coagulant before the fiber entered the outer coag-
ulation water bath. Furthermore, Figs. 3c and 4c also
reveal that the inner skin became denser and thicker
with increasing air gap, which could be attributed to
the enhanced gravity-induced elongational stress and

Table 2
Effect of air gap on properties of CA hollow fiber UF membranes
Membrane Air Outer Inner Wall Pure water flux Retention (%)
ID gap diameter diameter thickness (×10−5 l m−2 h−1 Pa−1 )
(mm) (␮m) (␮m) (␮m) PVP 10 K PVP 24 K BSA 66 K

M1 550 960 700 260 87.1 0.9 36.1 98

M2 880 940 700 240 68.2 5.2 55.4 100
 J.-J. Qin et al. / Journal of Membrane Science 218 (2003) 173–183 179

Fig. 4. SEM images of CA hollow fiber membrane spun from an air gap of 880 mm. (a) Overall, magnification: 75×; (b) partial cross-section,
magnification: 750×; (c) inner edge, magnification: 5000×; (d) outer edge, magnification: 5000×.

orientation on the inner skin in an increased air gap
[15,17,18]. The fiber with a denser and thicker skin
would result in a lower water flux and a higher solute
retention, which was supported by the latter results.
3.2.2. Effect of hypochlorite treatment
Figs. 5a and b show SEM images of inner and outer
surfaces of the fiber M2, respectively and Figs. 5c
and d show the corresponding inner and outer sur-
faces after the treatment with a hypochlorite solution
of 200 mg l−1 over 24 h. Comparing Fig. 5a and c, the
inner surface of the fiber appeared to become smooth
and the pores in the inner surface appeared to be larger
after the hypochlorite treatment. The porosity on the
outer surface of the treated fiber in Fig. 5d appeared
to be higher than that of the untreated fiber in Fig. 5b.
These changes in the membrane surface morphology
could be attributed to the removal of PVP contents in
the blend membrane. As a result, the treated fiber with
larger pore size would show a higher flux and a lower
retention and the treated fiber with less PVP contents
would show an increased fouling tendency, which was
also subsequently confirmed.
3.3. Fluxes and retentions of hollow fiber
membranes
3.3.1. Effect of air gap
Measurements of fluxes and retentions of hollow
fiber UF membranes spun from different air gap are
also summarized in Table 2. It can be seen that water
flux of a membrane decreased while retention in-
creased with increasing air gap due to the thicker and
denser inner skin layer of the fiber spun from higher
air gap as observed by SEM. Table 2 also shows
that the solute retention increased with an increase in
180 J.-J. Qin et al. / Journal of Membrane Science 218 (2003) 173–183

Fig. 5. Effect of hypochlorite treatment on surface morphology of CA hollow fiber membrane. (a) Untreated inner surface, magnification:
7500×; (b) untreated outer surface, magnification: 7500×; (c) treated inner surface, magnification: 7500×; (d) treated outer surface,
magnification: 7500×.

molecular weight of the solute used. Both membranes
gave high separations of albumin (MW 66 kg mol−1 )
or larger macromolecules from other bio-products
with lower molecular mass.
3.3.2. Effect of hypochlorite treatment
At first, the as-spun fibers were soaked in a
4000 mg l−1 hypochlorite solution for trial testing.
It was observed that the fibers were very weak and
fragile after being soaked in the hypochlorite solution
over 6 h, which confirmed that CA could not tolerate
high concentration of hypochlorite.
According to Roesink’s work [21], a hypochlorite
solution of 200 mg l−1 could cause a significant reac-
tion between hypochlorite and PVP 360 K. Therefore,
a hypochlorite solution of 200 mg l−1 was then se-
lected to treat the hollow fiber membranes over differ-
ent durations in this study. Measurements of fluxes and
retentions of M2 membranes, untreated and treated
over different durations are summarized in Table 3.
From the data, it could be seen that fluxes of the
treated membranes were about three times higher than
that of the untreated membrane while retentions of
the treated membranes were much lower than the un-
treated one, which indicated that the pore size in-
creased due to the hypochlorite treatment as shown in
Fig. 5. This could be attributed to the reaction between
hypochlorite and PVP in which the pyrrolidone ring of
PVP was mainly involved, causing chain scission of
PVP molecules and the eventual leaching of PVP from
the membrane after the treated fibers were rinsed in
water [19]. The results in this study were also in agree-
ment with the previous work [23–25] but differed from
Wienk et al. [22] who reported that the membrane pore
 J.-J. Qin et al. / Journal of Membrane Science 218 (2003) 173–183 181

Table 3
Effect of hypochlorite treatment time on pure water flux and solute retention of CA UF membranes
Membrane ID Treatment time (h) Pure water flux Retention (%)
(×10−5 l m−2 h−1 Pa−1 )
PVP 24 K BSA 66 K

M2 0 (untreated) 68.2 55.4 100

M2a 6 221 1.9 79
M2b 24 225 0 78

structure was not altered substantially by hypochlorite
treatment because membrane retentions for BSA were
found to be constant although the membrane water flux
increased after hypochlorite treatment. The difference
in observation may be due to the fact that the pore
size of their membranes after hypochlorite treatment
was possibly still too small for BSA passing through,
resulting in no significant change in retentions but the
pore size of the membranes in this study was signifi-
cantly increased after hypochlorite treatment, resulting
in an obvious change in retentions for BSA. It could
also be seen that there was no significant change in
both flux and retention for the membranes treated over
6 and 24 h, which suggested that there was an opti-
mum treatment time of less than 6 h to obtain a high
flux membrane. It is emphasized that both M2a and
M2b showed the same physical appearance in flexi-
bility as the untreated fiber M2, which was used as
an indication that the CA membrane tolerated these
hypochlorite treatments. However, when the treatment
time was 48 h, the CA membranes were attacked by
hypochlorite because the fibers became fragile.
3.4. Fouling tendency
Table 4 shows the experimental measurements of
Jvw , Jv , and Jva and the calculated Rm , Ra , σ Π
and Jrt of the membranes, untreated and treated with
hypochlorite. In the calculation, µ was assumed to
be 0.89 cPa of water viscosity at 25 ◦ C as the solu-
tion of 100 mg l−1 was very dilute. Rm was directly
calculated from Eq. (3). Ra was then obtained from
Eq. (5). And then σ Π was gained by substituting
Rm and Ra into Eq. (4). Finally, Jrt was obtained from
Eqs. (6) and (7) by substituting Rm , Ra and σ Π into
Eq. (6). For the untreated membrane M2, it could be
observed that the hydraulic resistance of the absorbed
layer (Ra ) was much smaller (around 200 times) than
that of the membrane (Rm ) and the osmotic pressure
(σ Π) was around 20 times lower than the operating
pressure (P). The total relative flux reduction (Jrt )
was low of 5.1% that was mainly caused by Π  (or
the osmotic pressure σ Π) as Ra was small accord-
ing to Eqs. (6) and (7). For the treated membrane M2a ,
however, Ra was only 22 times smaller than Rm and
σ Π was 18 times lower than P. Therefore, the to-
tal relative flux reduction Jrt was contributed by both
Ra and Π  as they were close. As a consequence,
Jrt was high of 9.4% that was around twice of the
untreated membrane. These results indicated that the
treated membrane showed higher fouling tendency due
to its higher resistance of the absorbed layer than the
untreated membrane, which may be partially caused
by the facts that the treated membrane had lower hy-
drophilicity due to the removal of PVP contents in
the membrane matrix after hypochlorite treatment and

Table 4
Rm , Ra , σ Π and Jrt of CA UF membranes with hypochlorite treatment
Membrane ID Solute Flux (×10−5 m s−1 ) Rm (m−1 ) Ra (m−1 ) σ Π (Pa) Jrt
Jvw Jv Jva

M2 BSA 1.493 1.416 1.485 7.81E+11 4.00E+09 4820 0.051

M2a BSA 5.512 4.995 5.361 2.15E+11 9.63E+09 5613 0.094
Note: P in the measurements of Jvw , Jv , and Jva was 104 kPa for the membrane M2 and was 105, 105 and 107 kPa, respectively, for the
membrane M2a .
182 J.-J. Qin et al. / Journal of Membrane Science 218 (2003) 173–183
had higher porosity than the untreated membrane as
shown in Fig. 5.
4. Conclusions
CA hollow fiber UF membranes were devel-
oped from a new dope solution containing CA/PVP
360K/NMP/water with a mass ratio of 19.0/5/74.8/1.2
using a dry-jet wet spinning process. The experimen-
tal results showed that water flux of a membrane
decreased while retention increased with increasing
air gap. Fluxes of treated membranes with hypochlo-
rite solution were about three times greater than
that of an untreated membrane and retentions of the
treated membranes were much lower. A 6 h treatment
with 200 mg l−1 hypochlorite solution could achieve
a CA membrane with a high pure water flux of
220 × 10−5 l m−2 h−1 Pa−1 . The experimental results
also showed that the treated CA membrane expe-
rienced higher fouling tendency than the untreated
membrane. SEM images revealed that PVP additive in
the dope would favor the suppression of macrovoids
and the thickness of inner skin increased with in-
creasing air gap. PVP contents in the blend mem-
brane could be significantly removed by hypochlorite
treatment and the pore size of the treated membrane
was increased. The latter observation differed from
published results and an attempt at explaining the
difference was given.
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