Journal of Membrane Science 208 (2002) 203–212

Poly(vinyl chloride) (PVC) hollow fiber ultrafiltration membranes

prepared from PVC/additives/solvent
Jian Xu, Zhen-Liang Xu∗
Chemical Engineering Research Center, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237,PR China
Received 4 February 2002; received in revised form 4 June 2002; accepted 4 June 2002

Abstract
Using poly(vinyl pyrrolidone) (PVP 40,000) or poly(ethylene glycol) (PEG) with different molecular weights (PEG 600,
PEG 800, PEG 1000) as additives and N,N-dimethylacetamide (DMAc) as a solvent, asymmetric poly(vinyl chloride) (PVC)
hollow fiber ultrafiltration membranes were prepared by phase inversion technique from 14 to 20 wt.% solids including PVC
and additives. The 95/5 DMAc/water and pure water were used as the bore fluid to investigate the effect of gelation bath.
The dope solutions, membrane structure, separation performance and mechanical properties of PVC hollow fiber membranes
were studied. The membrane structures of PVC hollow fiber membranes including external surface, internal surface and
cross-section were characterized by scanning electron microscopy (SEM), and the mechanical properties of PVC hollow
fiber membranes were discussed. It was found that using PVP or PEG as additives can increase the membrane porosity and
enhance the permeation flux by changing the membrane morphology. Three kinds of proteins having different molecular
weights were applied for the measurement of rejection. Based on the experimental results, pure water permeation fluxes of
PVC/additives/DMAc hollow fiber membranes might reach 100–200 l/(m2 h bar) while the molecular weight cut-off of PVC
hollow fiber membranes is approximately 50,000.
© 2002 Elsevier Science B.V. All rights reserved.
Keywords: Asymmetric hollow fiber membrane; Ultrafiltration; Poly(vinyl chloride); Additives; Membrane structure

1. Introduction because of its stiffness, low cost, excellent physical

and chemical properties, acids, alkalis and solvent re-
Ultrafiltration as a separation technology of high ef- sistance, as well as mechanical properties. Therefore,
ficiency and low energy consumption has widely been it is very likely that PVC is used to fabricate high
applied in various industries [1]. Numerous polymers performance ultrafiltration membranes in this case.
such as cellulose acetate (CA), polysulfone (PSf), Using phase inversion method, some researches
polyacrylonitrile (PAN), polyvinylidene difluoride have focused on the preparation of flat PVC ultrafiltra-
(PVDF), and polyetherimide (PEI) could be used to tion and microfiltration membrane [3–6]. Hirose and
prepare ultrafiltration membranes (flat or hollow fiber) co-workers investigated the preparation and structures
by inversion phase separation method [2]. Poly(vinyl of PVC membranes, and discussed the cause of phase
chloride) (PVC) is an outstanding membrane material separation process and the relationship between mem-
brane structure and phase separation process [3,4].
∗ Corresponding author. Tel.: +86-21-64252355; Using N,N-dimethylformamide (DMF) as a solvent
fax: +86-21-64252355. and water as a gelling non-solvent, the influence of
E-mail address: chemxuzl@ecust.edu.cn (Z.-L. Xu). PVC molecular weight on flat membrane structure and

0376-7388/02/$ – see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 6 - 7 3 8 8 ( 0 2 ) 0 0 2 6 1 - 2
204 J. Xu, Z.-L. Xu / Journal of Membrane Science 208 (2002) 203–212

separation performance was investigated by Bodzek DMAc were both analytical grade. Bovine serum al-
and Konieczny [6]. It was concluded that the greater bumin (MW = 67,000), chicken egg albumin (MW =
PVC molecular weight, the less concentrated casting 45,000) and lysozgme (MW = 14,400) were obtained
solution might be used to prepare flat membranes. from BIO LIFE Science & Technology Co. Ltd.
In the fabrication of flat PVC membranes, Some (Shanghai, PR China).
factors such as casting solution compositions, poly-
mer concentrations, solvents (N,N-dimethylacetamide 2.2. Mesurement of mixability parameter
(DMAc), DMF and tetrahydrofuran (THF)) and ad-
ditives (water, methanol, ethanol and n-propanol) Under different temperatures, water, methanol,
were studied by Hiroshi et al. [5] and Bodzek and ethanol and n-propanol were added to the PVC/DMAc
Konieczny [6]. Besides, other researchers reported solution as non-solvents to determine their composi-
the blends of PVC with other polymers to im- tions at which phase separation occurred. The binary
prove the PVC membrane performance. Ramesh polymer solution for titration tests contains 1 wt.%
Babu and Gaikar reported preparation, structure, PVC and 99 wt.% DMAc. The PVC/DMAc solution,
and transport properties of ultrafiltration membranes which is initially transparent, becomes opaque (cloud
from PVC/carboxylated poly(vinyl chloride) (CPVC) phenomenon) with the titration of non-solvents. The
blends and PVC/poly(vinyl pyrrolidone) (PVP) blends cloud phenomenon indicates the occurrence of phase
[7,8]. By changing the concentration of PVC in the separation of the polymer solutions while the cloud
DMF solution, they prepared the flat PVC membranes point was judged by visual observation. Based on the
from 10 to 12% (w/v). above titration of cloud point, the mixability parame-
However, the method of fabricating PVC hollow ter (MP) is calculated as follows:
fiber membranes through dry/wet-spinning technique Wnon-solvent
was seldom investigated previously. In this study, MP = (1)
Wnon-solvent + Wsolvent
asymmetric hollow fiber membranes were obtained
from a ternary solution of PVC, additives and DMAc where Wi is weight while subscript is non-solvent or
by wet phase inversion technique. Two different kinds solvent.
of additives, PVP and poly(ethylene glycol) (PEG),
are mixed with the polymer solution. PVC is a sort of 2.3. Preparations of PVC hollow fiber membranes
hydrophobic material, while PVP and PEG are both and modules
water-soluble polymers. In comparison with PVP
(40,000), the molecular weight of PEG (600, 800, Dry/wet-spinning technique, described elsewhere,
and 1000) is relatively low. The effect of different was used to fabricate hollow fibers [9–11]. The spin-
additives on membrane formation would be discussed neret has an outer diameter of 900 ␮m and an inner
later. Therefore, the investigation was focused on the diameter of 500 ␮m. Tables 1 and 2 summarize the
PVC dope solutions, membrane structure, and sepa- spinning conditions and outer diameter/inner diameter
ration performance of PVC ultrafiltration hollow fiber dimensions of the fabricated hollow fibers. Here, all
membranes. ratios of dope solution rates and bore fluid rates were
constant in all spinning processes. All nascent fibers
were not drawn (hence, no extension), which means
2. Experimental that the take-up velocity of the hollow fiber membrane
was nearly the same as the free falling velocity in the
2.1. Materials coagulation bath. After the formation of hollow fibers,
the fibers were stored in the water bath for at least
PVC resins, whose average degrees of polymeriza- 1 day to remove the solvents, and then immersed in
tion were 800 and 1000, respectively were obtained a tank containing 60% glycerol solution for at least
from Shanghai General Plant of Chloric Alkali (PR 1 day.
China). PVP (MW = 40,000) was obtained from Membrane modules were prepared to test the hollow
BASF (German). PEG (MW = 600, 800, 1000) and fiber separation performance in terms of permeation
 J. Xu, Z.-L. Xu / Journal of Membrane Science 208 (2002) 203–212 205

Table 1
Composition and spinning conditions of wet-spun hollow fiber membranes
Solution no. Polymer concentration (%) PVC/additives/solution ratio Bore fluid solution

1 14 14/86 (PVC/DMAc) 95/5 (DMAc/water)

2 19 14/5/81 (PVC/PVP/DMAc) Pure water
3 17 12/5/83 (PVC/PVP/DMAc) 95/5 (DMAc/water)
4 18 13/5/82 (PVC/PVP/DMAc) 95/5 (DMAc/water)
5 19 14/5/81 (PVC/PVP/DMAc) 95/5 (DMAc/water)
6 20 15/5/80 (PVC/PVP/DMAc) 95/5 (DMAc/water)
7 19 14/5/81 (PVC/PEG 600/DMAc) 95/5 (DMAc/water)
8 19 14/5/81 (PVC/PEG 800/DMAc) 95/5 (DMAc/water)
9 19 14/5/81 (PVC/PEG 1000/DMAc) 95/5 (DMAc/water)

flux and rejection quantitatively. Each module con- to the volume and weight of PVC hollow fiber mem-
sisted of 5–6 fibers with a length of 23 cm. The shell brane, the apparent density (ρ m ) of hollow fibers was
sides of the two ends of the bundles were glued onto obtained while the density (ρ a ) of intrinsic PVC is
two stainless steel tees using a normal-setting epoxy 1.4 g/cm3 [14]. Therefore, the porosity of membranes
resin. These modules were left overnight for curing (ε) is defined as
before tested. To eliminate the effect of the residual

ρm
glycerol on module performance, each module was ε (%) = 1 − × 100 (2)
immersed in water for 1 day and run in the test system ρs
for 1 h under a pressure of 1 bar before any sample
collection. 2.5. Measurement of pure water permeation flux and
protein (bovine serum albumin, chicken egg albumin
and lysozgme) rejection
2.4. Measurement of membrane porosity
Fig. 1 shows a schematic diagram of protein–water
The porosity of the hollow fibers was determined
separation membrane unit. At a transmembrane pres-
by the mass loss of wet membranes after drying [13].
sure of 1 bar and room temperature, all experiments
The outer, inner diameters and length of a hollow fiber
were performed in hollow fiber modules. Two mod-
sample were measured under wet status, and then its
ules were prepared for each hollow fiber sample, and
volume was calculated. This sample was dried in vac-
the final result of each sample is the average value of
uum until a constant mass is obtained. Then the sam-
them.
ple was weighed by an analytical balance. According
Pure water permeation flux (PWP, Jw ) of hollow
fiber membranes was obtained as follows:
Qw
Table 2 Jw = (3)
Diameter of wet-spun hollow fiber membranes
P A
Solution o.d. Thickness i.d. o.d./i.d. where Jw is the permeation flux of membrane
no. (␮m) (␮m) (␮m) ratio (l/(m2 h bar); Qw the volumetric flow rate of solution
1 807 124 559 1.44 (l/h);
P the transmembrane pressure drop (bar); A
2 930 124 740 1.26 is the membrane outer surface area (m2 ).
3 1160 286 600 1.93
4 1120 270 580 1.93
Two liters of 0.05 wt.% protein solution in deion-
5 970 199 570 1.70 ized water was used for the measurement of protein
6 930 186 550 1.69 rejection of each hollow fiber module. To realize the
7 932 186 559 1.67 separation efficiency for different molecular weight,
8 981 211 559 1.75 three kinds of proteins, bovine serum albumin (MW =
9 932 156 621 1.51
67,000), chicken egg albumin (MW = 45,000) and
206 J. Xu, Z.-L. Xu / Journal of Membrane Science 208 (2002) 203–212

Fig. 1. Schematic diagram of protein–water membrane separation.

lysozgme (MW = 14,400), were applied, respectively. 3. Results and discussions

Apparent rejection (R) was the fraction of one species
of molecules, which was retained and was expressed 3.1. Effects of various non-solvents on the phase
as separation
Cp
R =1− (4)
C0 As shown in Fig. 2, the cloud point curves present
that the relationships between mixed parameters (MP)
where Cp is the concentration of protein in the per- of PVC/DMAc solutions with four non-solvents (wa-
meation and C0 is the initial concentration of protein. ter, methanol, ethanol and n-propanol) are obtained
The concentration of protein was determined based from 20 to 50 ◦ C. It is found that the MP values of
on absorbance in UV-spectrophotometer (Shimadzu four non-solvents increase as follows: n-propanol >
UV3000, Japan) at wavelength of 280 nm. ethanol > methanol > water. In fact, when non-sol-
vents are added to the PVC/DMAc solutions, the
2.6. scanning electron micrograph (SEM)

To avoid destroying the structure of the cross-sec-

tions of hollow fibers, membrane samples for scan-
ning electron microscopy (SEM) were first immersed
in liquid nitrogen, fractured and then sputtered with
metallic gold to obtain an adequate contrast of the
membrane fracture. A CAMBRIDGE S-250 field
emission SEM was used to investigate the morphol-
ogy of hollow fiber membranes.

2.7. measurements of mechanical properties

of PVC hollow fiber membranes

Tensile properties of PVC hollow fiber membranes

were measured at 50 mm gauge length using an Instron
test unit (model: INSTRON 4442). The test method
was based on ASTM measurements. At least five Fig. 2. The relationship between MP and temperature in PVC/
samples were tested for each experimental result. DMAc solutions.
 J. Xu, Z.-L. Xu / Journal of Membrane Science 208 (2002) 203–212 207

Table 3 PVP or PEG. During the phase separation process,

The solubility parameters of PVC, solvents and non-solvents [12] a one-phase dope solution (PVC/additives/DMAc) is
Substance δd δp δh δ sp converted into two-phase system consisting of a solid
(MPa)1/2 (MPa)1/2 (MPa)1/2 (MPa)1/2 phase (PVC-rich) that forms the membrane structure
DMAc 16.8 11.5 10.2 22.7 and a liquid phase (PVC-poor) that forms the pores in
NMP 18.0 12.3 7.2 22.9 the final membrane.
Water 15.5 16.0 42.4 47.9
The membrane structures of the cross-section of
Methanol 15.1 12.3 22.3 29.7
Ethanol 15.8 8.8 19.4 26.6 PVC hollow fiber membranes wet-spun form nos. 1,
Propanol 16.0 6.8 17.4 24.6 2, 5, and 9 dope solutions are shown in Fig. 3. It
PVC 18.7 10.0 3.1 can be seen from Fig. 3 that the PVC hollow fiber
membrane nos. 1 and 9 have the similar structure, a
finger-like shape over the entire cross-section of the
thermodynamic status in the PVC/DMAc solutions is membrane, adjoining each other sparsely. However,
changed because the solubility of solvent is weakened. compared with membrane no. 1 prepared without any
The higher the solubility parameter disparity of sol- additive in the dope solution, membrane no. 9 made
vent and non-solvent, the more intense the interaction with PEG has a more porous structure consistent with
of solvent with non-solvent and the faster the solubil- later results. Therefore, the presence of PEG in the
ity of solvent to polymer will decline. If non-solvents dope solution might improve the membrane structure
have a strong effect on PVC, the precipitation of PVC and enhance PVC membrane performance. Mem-
will occur more easily. From the solubility parame- brane no. 2 exhibits a two-layer fingerlike structure
ters (δ sp ) of non-solvents listed in Table 3, it is found extended to the middle of the cross-section because
that the δ sp values of non-solvents have the following pure water was used as both the inner and outer
order: water > methanol > ethanol > n-propanol, precipitant. The cross-section of membrane no. 5
while the hydrogen-bonding parameters (δ h ) have consists of large voids in the shape of spheres or el-
also the same order. The experimental results of lipsoids, and between these voids there is a spongy
non-solvent cloud points coincide with the predictions structure. The large voids make membrane no. 5 more
of solubility parameter theory, i.e. the weak interac- porous than membrane nos. 1, 2, and 9 due to the
tion of solvents with non-solvents leads to a higher presence of PVP as the additive of a water-soluble
value of MP. In this case, water is chosen as the gela- polymer.
tion bath for the exchange of the solvent system due Fig. 4 shows the SEM images of the external struc-
to its intense interaction with the solvent (DMAc) and tures of hollow fiber membranes wet-spun form nos.
low MP value. 1, 2, 5, and 9 dope solutions listed in Table 1. In Fig. 5,
the external surface structure of the PVC membrane
3.2. Membrane morphology of PVC hollow fiber (membrane no. 1) prepared without additives in the
membranes dope solution looks more ragged, while membrane
nos. 2, 5, and 9 obtained with additives looks more
Generally, an asymmetric membrane with a dense smooth, especially membrane no. 5 with the PVP.
skin supported by a porous substructure is obtained The experimental results illustrate that the precipita-
when the spun dope polymer solution is immersed di- tion of PVC forming the membrane external surfaces
rectly into a non-solvent bath. This skin, formed due and the exchange of solvents with non-solvents may
to the differences in solution rates and diffusion rates be affected by the diffusion of the water-soluble ad-
of the components in the membrane formation, plays ditives (PEG and PVP) from the dope solution to the
an essential and crucial role in many membrane sep- water bath. Besides, there are more and large cracks
aration processes such as reverse osmosis, gas sepa- in membrane nos. 2 and 5 that use PVP as additives
ration, and pervaporation. For the ultrafiltration mem- whereas few cracks can be found on the membrane
brane, a skin with 1–50 nm pore has to be present. In surface of nos. 1 and 9. Since the separation perfor-
this case, PVC hollow fiber ultrafiltration membranes mance of hollow fiber membranes is largely deter-
are prepared from a dope solution containing PVC and mined by the surface structure, this can explain why
208 J. Xu, Z.-L. Xu / Journal of Membrane Science 208 (2002) 203–212

Fig. 3. Scanning electron micrograph of the cross-section structures of PVC hollow fiber membranes wet-spun form nos. 1, 2, 5, and 9
dope solutions, respectively (original magnification: 200×).

membranes produced with PVP as additives result additives is distinct from those prepared in the pres-
in high permeation fluxes (listed in Table 4) whereas ence of the additives and different bore fluid solu-
no. 1 membrane has the lowest flux. tions also result in different structures. The pore size
From Fig. 5, it is found that the morphology of of membrane no. 1 without additives in the internal
membrane internal surface structure in the absence of surface is much larger than that of membrane no. 9
with PEG and membrane no. 5 with PVP. The exper-
imental result may suggest that, like the formation of
Table 4 external surface structure, the presence of additives
Porosity, permeation fluxes and rejection of proteins for PVC plays an important role in the formation of internal
hollow fiber membranes
structure by altering the precipitation of PVC and the
Membrane Porosity Jw (l/(m2 h bar)) Rejection exchange of solvents with non-solvents. The internal
no. (%)
BSA CEA Lysozgme layer of membrane no. 2 prepared with pure water as
(%) (%) (%) bore fluid is so dense that no pores could be found
1 73.2 23 99 91 59 on the internal surface even under the magnification
2 78.8 96 99 79 13 of 5000, while membrane nos. 1, 5, and 9 show fully
3 90.3 201 99 93 63
4 89.7 178 99 98 47
porous surfaces using 95/5 DMAc/water as bore fluid.
5 86.9 166 99 93 37 This is because solvent concentration in the bore fluid
6 83.7 155 99 87 15 results in delayed demixing for the internal layer due
7 82.0 59 99 87 67 to the less solubility parameter disparity of the sol-
8 84.5 80 99 84 49 vent and the precipitant (the bore fluid) [2]. It is well
9 81.5 84 99 84 71
known that the larger the pore size is, the less the
 J. Xu, Z.-L. Xu / Journal of Membrane Science 208 (2002) 203–212 209

Fig. 4. Scanning electron micrograph of the external structures of PVC hollow fiber membranes wet-spun form nos. 1, 2, 5, and 9 dope
solutions, respectively (original magnification: 5000×).

resistance can be encountered. In comparison with the 600), membrane no. 8 (PEG 800), and membrane no.
external skin which represents the selective layer, the 9 (PEG 1000) it can be concluded that PVP, used
internal surface and porous layer of hollow fiber mem- as an additive, can increase the membrane porosity
branes which serve only as a support for he selective greatly. The porosity of PVC hollow fiber membrane
layer have little effect on the separation characteris- is also largely dependent on the concentration of
tic or the mass transfer rate of the membrane. This PVC in the dope solutions. The PVC hollow fiber
may illustrate why membrane no. 1 with the largest membranes prepared from a lower concentration of
pore size of internal surface has the lowest permeation PVC polymer show a greater porosity. With an in-
fluxes. crease in the concentration of polymer solutions, the
polymer chains and the higher viscosity of polymer
3.3. Separation performance of PVC hollow fiber solutions prohibit the exchange of the solvent system
membrane for non-solvents through the phase separated polymer
solution. Besides, it can be seen from membrane no.
The separation characteristics of PVC/additives/ 2 (the porosity = 78.8%) and membrane no. 5 (the
solvents hollow fiber membranes such as the poros- porosity = 86.9%) that the bore fluid solution ex-
ity, permeation fluxes and rejections were given in erts a considerable influence on the porosity of PVC
Table 4. The compositions of polymer solutions and hollow fiber membranes. The rapid precipitation of
wet-spinning conditions that determine the mem- PVC polymers caused by pure water as a bore fluid
brane structures and performance were summarized solution generates a thin skin layer that limits the
in Table 1. From membrane no. 1 (without any addi- exchange of the solvent system for non-solvents and,
tive), membrane no. 5 (PVP), membrane no. 7 (PEG thus, suppresses the pore formation in the membranes.
210 J. Xu, Z.-L. Xu / Journal of Membrane Science 208 (2002) 203–212

Fig. 5. Scanning electron micrograph of the internal structures of PVC hollow fiber membranes wet-spun form nos. 1, 2, 5, and 9 dope
solutions, respectively (original magnification: nos. 1, 5, and 9, 500×; no. 2, 5000×).

Table 4 also shows that high porosities of hollow also affect the membrane performance. The large pore
fiber membranes were consistent with high perme- structure obtained from lower concentration or with
ation fluxes and low rejection because low porosity the PVP additive (membrane nos. 3 and 4) shows more
and dense skin may result in a higher resistance for open and porous structures in the support whereas the
water permeation and greater rejection. Except poros- finger-like structure prepared from higher concentra-
ity, however, some other factors such as the properties tion or the absence of the additives (membrane nos. 1
of polymer materials and the inner structure of hol- and 6) shows a more thicker and compact skin layer.
low fiber membranes may also have great influence Although PEG as a low molecular weight additive
on the permeation fluxes and rejection of hollow fiber (membrane nos. 7–9) could improve the permeation
membranes. Generally, UF membranes prepared from fluxes of PVC membranes, PVP as a high molecular
hydrophilic polymer materials often exhibit higher weight additive (membrane nos. 3–6) is more sig-
permeation fluxes than those from hydrophobic ma- nificant and effective. Besides, mass transfer of the
terials. Since PVC is a hydrophobic material, PVP gelation bath plays an important role in determining
containing highly hydrophilic amide groups, was used the structure of the membranes. Mass transfer mainly
an additive for the preparation of PVC hollow fiber happens at the interface (the outer and inner surface of
membranes. Results of membrane no. 1 (without PVP, hollow fiber membranes) between the polymer solu-
the flux = 19 l/(m2 h bar)) and membrane no. 5 (PVP tion and the gelation medium by diffusion process. Ex-
as an additive, the flux = 166 l/(m2 h bar)) are con- change of the solvent system for non-solvents across
sistent with what have been predicted. The size and the interface introduces a phase separation, leading
shape of the pore depending on the composition of the to different membrane structures by varying gela-
polymer solution and the dry/wet-spinning conditions tion medium. Pure water and water/DMAc solution
 J. Xu, Z.-L. Xu / Journal of Membrane Science 208 (2002) 203–212 211

were used as two kinds of bore fluid solutions to determined by the PVC solid content in the mem-
investigate the role of gelation medium. brane, while the presence of additives has little effect
It can be observed from Table 4 that the rejection on it. From Table 4, it can be seen the effect of the
for bovine serum albumin (MW = 67,000) of all PVC bore fluid on hollow fiber membrane properties. Us-
hollow fiber membranes is very high (more than 99%) ing pure water as the bore fluid, membrane no. 2 has
and have no difference, which shows that all bovine the highest mechanical properties. This phenomenon
serum albumin molecules can be retained by PVC was due to the fact that pure water is a powerful co-
hollow fiber membranes. But the rejection of chicken agulation agent, which tends to form another thick or
egg albumin (MW = 45,000) varies from 79 to 98% dense inner layer as shown in Fig. 5.
while the rejection of lysozgme (MW = 14,400) varies
from 13 to 71%. From above experimental results, the
4. Conclusions
molecular weight of rejection might be considered as
50,000. PVC hollow fiber membrane prepared with PVC was used as the membrane material and
PVP as an additive has a higher rejection than that PVP (MW = 40,000), PEG with different molecu-
prepared with PEG. The membrane morphologies in lar weights (PEG 600, PEG 800, PEG 1000) as the
Figs. 3–5 can explain these experimental results. additives, asymmetric PVC hollow fiber membranes
were wet-spun from 14 to 20 wt.% solids solutions.
3.4. Mechanical properties of PVC hollow fiber The spun dope solution is immersed directly into a
membranes water bath. The effect of different additives, polymer
solutions on membrane structure, permeation flux
In order to evaluate the mechanical properties of
and protein–water separation performance, mechani-
PVC hollow fiber membranes in the industrial appli-
cal properties of PVC/additives/DMAc hollow fiber
cations, the values of tensile strength and elongation
membranes were studied. The 95/5 DMAc/water so-
of hollow fiber membranes were determined. Table 5
lution was used as bore fluid to form hollow fiber
shows the mechanical properties of PVC hollow fiber
membrane with skinless internal layer, and pure water
membranes. Within the experimental error, tensile
was used as another bore fluid to form denser inter-
strength at break, elongation at break and Young’s
nal skin. SEM images illustrated that the presence of
modulus of PVC hollow fiber membrane seems to
PVP or PEG as an additives could result in the change
be approximately depended on the porosity of mem-
of the hollow fiber membrane structure. PVC hollow
branes, decreasing with the increase of hollow fiber
fiber membranes with higher porosity exhibit higher
porosity. And the membranes of similar porosity pre-
permeation fluxes, lower rejections for protein, and
pared from various polymer solution (nos. 1 and 2;
lower mechanical properties. From the experimental
nos. 6 and 7; nos. 8 and 9) shows similar mechani-
results obtained, the PVC/additives/DMAc hollow
cal properties. This may suggest that the mechanical
fiber membranes have pure water permeation fluxes
properties of PVC hollow fiber membranes are mainly
of 100–200 l/(m2 h bar), and the molecular weight
cut-off of the membranes is approximately 50,000.
Table 5
Mechanical properties of hollow fiber membranes
Membrane Break strength Elongation at Young’s Acknowledgements
no. (MPa) break (%) modulus (MPa)
1 3.0 ± 0.3 46.7 ± 2.8 136.6 ± 7.1 Contract grant sponsored by National Nature Sci-
2 4.3 ± 0.2 33.6 ± 1.9 156.9 ± 10.2 ence Foundation (Grant no. 20076009).
3 1.3 ± 0.1 14.3 ± 0.9 56.9 ± 3.9
4 1.4 ± 0.0 16.6 ± 0.8 53.1 ± 4.2
5 1.9 ± 0.1 24.0 ± 2.4 85.8 ± 6.8
References
6 1.9 ± 0.1 11.4 ± 0.6 95.0 ± 8.9
7 2.2 ± 0.5 13.2 ± 1.5 101.0 ± 9.4 [1] R. Rautenbach, R. Albrecht, Membrane Processes, Wiley,
8 2.3 ± 0.1 14.2 ± 1.4 101.0 ± 5.9 New York, 1981.
9 1.8 ± 0.2 8.7 ± 1.0 117.6 ± 10.6 [2] R.E. Kesting, Synthetic Polymeric Membranes, Wiley, New
York, 1985.
212 J. Xu, Z.-L. Xu / Journal of Membrane Science 208 (2002) 203–212

[3] S. Hirose, A. Shimizu, T. Nose, Preparation and structures of chloride) and poly(vinyl pyrrolidone) blends, J. Appl. Polym.
the poly(vinyl chloride) porous membranes, J. Appl. Polym. Sci. 77 (2000) 2606.
Sci. 23 (1979) 3193. [9] Z.L. Xu, T.S. Chung, Y. Huang, Effect of poly(vinyl pyrro-
[4] S. Hirose, E. Yasukawa, Wet poly(vinyl chloride) membranes, lidone) molecular weights on morphology, oil/water separ-
J. Appl. Polym. Sci. 26 (1981) 1039. ation, mechanical and thermal properties of polyetherimide/
[5] O. Hiroshi, R. Kazuhiko, U. Tadashi, Influence of casting poly(vinyl pyrrolidone) hollow fiber membranes, J. Appl.
solution additive, degree of polymerization, and polymer Polym. Sci. 74 (1999) 2220.
concentration on poly(vinyl chloride) membrane properties [10] Z.L. Xu, T.S. Chung, K.C. Loh, B.C. Lim, Polymeric
and performance, J. Membr. Sci. 83 (1993) 199. asymmetric membranes made from PEI/PBI/PEG for oil–sur-
[6] M. Bodzek, K. Konieczny, The influence of molecular mass factant–water separation, J. Membr. Sci. 158 (1999) 41–53.
of poly(vinyl chloride) on the structure and transport char- [11] I.M. Wienk, H.A. Teunis, T. Van den Boomgaard, C.A.
acteristics of ultrafiltration membranes, J. Membr. Sci. 61 Smolders, A new spinning technology for hollow fiber
(1991) 131. ultrafiltration membranes, J. Membr. Sci. 78 (1993) 93.
[7] P. Ramesh Babu, V.G. Gaikar, Preparation, structure, and [12] J. Brandrup, E.H. Immergut, Polymer Handbook [M], 3rd
transport properties of ultrafiltration membranes of poly(vinyl Edition, Wiley, New York, 1989.
chloride) (PVC), carboxylated poly(vinyl chloride) (CPVC), [13] Z.L. Xu, X.D. Zhan, G.E. Chen, Study on high-porosity poly
and PVC/CPVC blends, J. Appl. Polym. Sci. 73 (1999) (vinylidene fluoride) hollow fiber ultrafiltration membranes,
1117. Membr. Sci. Technol. 20 (4) (2000) 10–16.
[8] P. Ramesh Babu, V.G. Gaikar, Preparation, structure, and [14] J. Brandrup, E.H. Immergut, Polymer Handbook [M], 4th
transport properties of ultrafiltration membranes of poly(vinyl Edition, Vol. 67, Wiley, 1999.