Journal of Membrane Science 337 (2009) 257–265

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Journal of Membrane Science

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

Preparation and characterization of PVDF–SiO2 composite hollow fiber UF

membrane by sol–gel method
Li-Yun Yu a,b , Zhen-Liang Xu a,b,∗ , Hong-Mei Shen b , Hu Yang b
a
State Key Laboratory of Chemical Engineering, East China University of Science and Technology (ECUST), 130 Meilong Road, Shanghai 200237, China
b
Membrane Science and Engineering R&D Lab, Chemical Engineering Research Center, ECUST, 130 Meilong Road, Shanghai 200237, China

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

Article history: Organic–inorganic polyvinylidene fluoride (PVDF)–silica (SiO2 ) composite hollow fiber ultrafiltration (UF)
Received 30 November 2008 membranes were prepared by the combination of a tetraethoxysilane (TEOS) sol–gel process with a
Received in revised form 23 March 2009 wet-spinning method. The membrane formation mechanisms were investigated in terms of viscosity,
Accepted 30 March 2009
precipitation kinetics and morphology. Results showed the dope viscosity increased with the increment
Available online 9 April 2009
of TEOS concentration in dope. The addition of TEOS accelerated the precipitation of the dope. SEM
pictures showed the cross-section morphology of PVDF composite membranes changed from finger-like
Keywords:
macrovoids to sponge-like structure with increasing SiO2 content. The mechanical, thermal stabilities and
Organic–inorganic
Polyvinylidene fluoride
permeation property of PVDF–SiO2 composite membranes were further examined. At lower TEOS con-
Silica centration, the hydrolyzed SiO2 particles, which were homogeneously dispersed in PVDF matrix, acted
Hollow fiber UF membrane as the physical crosslinking points, and led to an improvement of mechanical and thermal properties.
Sol–gel process While at higher TEOS concentration, SiO2 formed network, which restricted the movement of PVDF and
led to the decrease of the mechanical and thermal stabilities. Moreover, XRD and FTIR results revealed
that the crystal structure of PVDF underwent a transition from ␣-phase to ␤-phase due to the addition
of TEOS. The contact angle and UF experimental results of PVDF–SiO2 composite membranes showed
an improvement of hydrophilicity and permeability. The PVDF–SiO2 membrane prepared from the dope
with 3 wt.% TEOS concentration had the best UF performance and antifouling property.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction Polyvinylidene fluoride (PVDF) is one of the most extensively

Currently, polymers are still the main materials in membrane
technology with the advantages of good membrane forming ability,
flexibility and low cost [1–3]. However, limited chemical, mechan-
ical and thermal resistance restrict the application of polymer
materials [4–6]. As reported in literatures [7,8], ceramics mem-
branes have higher thermal and chemical resistance as well as
longer lifetime, but they are still expensive and brittle with poor
membrane forming ability. Composite materials could combine
basic properties of organic and inorganic materials and offer spe-
cific advantages for the preparation of artificial membranes with
excellent separation performances, good thermal and chemical
stability and adaptability to the harsh environments, as well as
membrane forming ability [9–12]. Therefore, organic–inorganic
composite materials as new membrane materials have attracted
more and more attentions [13,14].
∗ Corresponding author at: State Key Laboratory of Chemical Engineering, East
China University of Science and Technology (ECUST), 130 Meilong Road, Shanghai
200237, China. Tel.: +86 21 64252989; fax: +86 21 64252989.
E-mail address: chemxuzl@ecust.edu.cn (Z.-L. Xu).
applied membrane materials in the industry for outstanding antiox-
idation, superior thermal and hydrolytic stabilities, as well as
good mechanical and membrane forming properties. However, its
hydrophobic nature that often results in severe membrane fouling
and decline of permeability, has been a barrier for their application
in water treatment [15]. Many studies have attempted to improve
the hydrophilicity of PVDF membranes with various techniques,
such as physical blending, chemical grafting and surface modifica-
tion [16]. Among these methods, blending with inorganic materials
is interesting due to its convenient operation and mild condition
[17].
Inorganic materials that could be blended with PVDF include
titanium dioxide (TiO2 ) [18], zirconium dioxide (ZrO2 ) [19], alu-
mina (Al2 O3 ) [20] and some small molecule inorganic salts, such
as lithium salts [21]. Among the numerous inorganic materials, sil-
ica (SiO2 ) is the most convenient and widely used because of its
mild reactivity and well-known chemical properties [22]. A simple
method to obtain an organic–inorganic hybrid is mixing an organic
polymer with a metal alkoxide, such as tetraethoxysilane (TEOS),
followed by a sol–gel process involving hydrolysis and polyconden-
sation of TEOS [23]. Recently, the sol–gel technique has provided
new opportunities for the preparation of organic–inorganic materi-

0376-7388/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2009.03.054
258 L.-Y. Yu et al. / Journal of Membrane Science 337 (2009) 257–265
als, which allows the formation of inorganic framework under mild
condition and incorporation of minerals into polymers, resulting
in increased chemical, mechanical and thermal stabilities without
obviously decreasing the properties of the polymers [24,25]. Fur-
thermore, the remaining hydrogen bond clusters at the surfaces
of the materials after the sol–gel reaction improve the membrane
hydrophilicity and enhance the stability of composite materials
[26–30].
In this work, organic–inorganic PVDF–SiO2 composite hol-
low fiber UF membranes were prepared by sol–gel process and
wet-spinning method. The objective of this work was to system-
atically reveal the viscosity and precipitation kinetics, morphology,
mechanical and thermal properties, crystalline structure, as well
as hydrophilicity and permeability of the PVDF–SiO2 composite
hollow fiber UF membranes.
2. Experimental
2.1. Materials
PVDF (Solef® 1015) was purchased from Solvay Advanced
Polymers, L.L.C. N,N-dimethylacetamide (DMAc), N,N-dimethyl-
formamide (DMF) and tetraethoxysilane (TEOS) were all obtained
from Shanghai Chemical Reagent Company. Hydrochloric acid (HCl,
36–38%) was of analytical grade (from Beijing Chemical Reagent
Company) and used as received. Bovine serum albumin (BSA)
(Mw = 67,000) was purchased from Shanghai Bio Life Sci and Tech
Co. Ltd.
2.2. Preparation of hollow fiber membrane and module
13.1 mL TEOS and 1.8 mL deionized water were added to 18.1 mL
DMF with vigorous stirring for 2 h at 25 ◦ C. After mixing uniformly,
stable and transparent SiO2 sol was obtained with pH 3.0 adjusted
by hydrochloric acid.
SiO2 sol with different concentration (0, 1, 2, 3, 4 and 5 wt.% TEOS
in dopes, which were labeled as MTEOS-0, MTEOS-1, MTEOS-2,
MTEOS-3, MTEOS-4 and MTEOS-5, respectively) was added drop-
wise to the dope of DMAc containing 18 wt.% PVDF with constant
stirring at 25 ◦ C for 24 h to get a homogenous PVDF–SiO2 dope for
spinning.
PVDF–SiO2 hollow fiber UF membranes were spun by wet-
spinning method at 25 ◦ C, described elsewhere [13,31]. The bore
fluid solution and coagulant were 40 wt.% ethanol aqueous solution
and pure water, respectively. The fabricated hollow fiber mem-
branes were kept in the water bath for 24 h to remove the residual
solvents, and then immersed in a tank containing 50 wt.% glyc-
erol aqueous solution for 24 h to prevent the collapse of porous
structures [32]. And the membranes were dried in air at room tem-
perature for making test modules.
Membrane modules were prepared to test the hollow fiber sep-
aration performances in terms of permeation flux and rejection
quantitatively. The hollow fiber UF membrane modules were self-
Fig. 1. Preparation method for PVDF–SiO2 composite hollow fiber membranes.
prepared (outside feeding), and the external diameter and inner
diameter of the pipeline were 0.8 and 0.6 cm, respectively. Four hol-
low fibers with an effective length of 22.5 cm were composed into
a module. The shell sides of the two ends of the bundles were glued
onto two stainless steel tees using a normal-setting epoxy resin.
These modules were left overnight for curing before test. To elimi-
nate the effect of the residual glycerol on module performance, each
module was immersed in water for 24 h and run in the test system
for 1 h under a pressure of 0.1 MPa before any sample collection.
The schematic outline of the sample preparation was illustrated in
Fig. 1.
2.3. Membrane characterization
2.3.1. Viscosity and light transmittance measurements
The viscosity of dopes with different TEOS concentrations was
investigated by a DV-II+PRO Digital Viscometer (Brookfield, USA) at
25 ◦ C controlled by water bath.
Light transmittance measurement studying precipitation kinet-
ics was a self-made device. The experiments were described by Li
et al. [33]. The light source of laser was directly exposed to a dope,
about 20 cm above it. The dope was immersed into the water bath
used as coagulation fluid. The transmitted light was detected by
an optical detector. The accepted signal was then A/D converted,
amplified and recorded by a computer. The intensity of the trans-
mitted light through the dope was measured as a function of time.
2.3.2. Morphology observation
The morphology of membranes was examined by a scanning
electron microscopy (SEM) (JEOL Model JSM-6360 LV, Japan). The
fibers were firstly immersed into liquid nitrogen for a few min-
utes, then broken and deposited on a copper holder. All samples
were coated with gold under vacuum before test. For the same sam-
ples of SEM, the map scan spectrum of energy dispersion of X-ray
(EDX) (EDAX Falcon, USA) was applied to detect the particle dis-
tribution profile on the external surface of the PVDF–SiO2 hollow
fiber membrane.
2.3.3. Mechanical properties and thermal stability analyses
Mechanical properties of membranes were measured by a mate-
rial test machine (SHIMADZU, Japan) at a loading velocity of
50 mm/min. The report values were measured 3 times for each sam-
ple and then averaged. The thermal stability of membranes was
evaluated by thermal gravitational analysis (TGA, TA SDT-Q600,
USA). The TGA measurements were carried out under nitrogen
atmosphere at a heating rate of 10 ◦ C/min from 50 to 800 ◦ C.
2.3.4. X-ray diffraction (XRD) and FTIR analyses
The membrane XRD patterns were recorded on a D/max-rB
diffractometer (Rigaku, Japan) equipped with graphite monochro-
mated Cu K˛ radiation ( = 0.15405 nm) operated at 50 mA and
50 kV from 10◦ to 80◦ . The FTIR spectra of the membranes
were measured using a FTIR-ATR spectrometer (Thermo Electron
 L.-Y. Yu et al. / Journal of Membrane Science 337 (2009) 257–265 259

Corp., Nicolet 5700, USA) operating in the wavenumber range CP and CF were the permeate and feed concentration, respectively
4000–400 cm−1 . (wt.%).
The membrane surface morphology, in terms of the mean sur-
2.3.5. Hydrophilicity, porosity and pore size measurements face roughness (Ra ), was measured by an atomic-force microscopy
The contact angle () between water and the external surface of (BioScopeTM , USA) using the tapping mode. The mean roughness
hollow fiber membrane was measured to evaluate the membrane was defined as the average value of the surface relative to the cen-
hydrophilicity using a JC2000A Contact Angle Meter produced by ter plane for which the volumes enclosed by the images above and
Shanghai Zhongcheng Digital Equipment Co., Ltd. (China). To mini- below the plane were equal. This parameter was calculated using
mize experimental error, the contact angles were measured 5 times the following equation [16]:
 
for each sample and then averaged. The membrane porosity ε (%)
1
Lx Ly  
was defined as the volume of the pores divided by the total volume Ra = f (x, y) dxdy (6)
Lx Ly
of the porous membrane. It could usually be determined by gravi- 0 0

metric method, determining the weight of liquid (here pure water) here f(x, y) was the surface relative to the central plane, and Lx and
contained in the membrane pores [33]. Ly were the dimensions of the surface.
(w1 − w2 )/dw
ε= × 100% (1) 3. Results and discussion
(w1 − w2 )/dw + w2 /dp

where w1 was the weight of the wet membrane (g), w2 was the 3.1. Viscosity and precipitation kinetics of dopes
weight of the dry membrane (g), dw was the pure water density
(0.998 g cm−3 ) and dp was the polymer density (as the inorganic The viscosity of dope influenced the exchanging rate of sol-
content in the membrane matrix was small and dp was approximate vent and non-solvent through the dope, furthermore changed the
to dPVDF , namely 1.765 g cm−3 ). hydrolysis and condensation rate of TEOS during phase inver-
Mean pore radius rm (␮m) was determined by filtration velocity sion. The demixing rate played an important role in the formation
method. According to Guerout–Elford–Ferry equation, rm could be of microstructures and performances of the membranes [36]. In
calculated [34]: Fig. 2, the viscosity of PVDF dopes increased with the increment of
 TEOS concentration. The addition of SiO2 sol in the PVDF solution
(2.9 − 1.75ε) × 8lQ increased the concentration of the dope, and consequently inten-
rm = (2)
ε × A × P sified the interaction force among PVDF macromolecules [36]. At
the same time, because the hydroxyl groups of SiO2 sol might have
where  was the water viscosity (8.9 × 10−4 Pa s), l was the mem-
a stronger adsorption on polymeric chains [24] and SiO2 sol had a
brane thickness (m), Q was the volume of the permeate water per
higher viscosity [36], the dope viscosity increased at higher TEOS
unit time (m3 s−1 ), A was the effective area of the membrane (m2 )
concentration.
and P was the operational pressure (0.1 MPa).
Light transmittance experiment was used for the investigation
Maximum pore size rmax (␮m) could be obtained by bubble point
of the precipitation kinetics of dopes. The pure water was used as
method. According to Laplace’s equation, maximum pore size could
the coagulation bath. In Fig. 3, the addition of TEOS accelerated the
be calculated [35]:
demixing process, in particular, the precipitation rate reached the
2 cos  highest at 3 wt.% TEOS in dope.
rmax = (3)
P As shown in Fig. 3, the precipitation rate firstly increased and
then decreased with increasing TEOS concentration. This phe-
where  was the surface tension of water (71.96 × 10−3 N m−1 ), 
nomenon was related to the counterpart effects of TEOS. Generally
was the contact angle of water to membrane (◦ ) and P was the
the addition of hydrophilic substance in the dope led to an acceler-
minimum bubble point pressure (Pa).
ation of solvent and non-solvent exchange and was advantageous
to form a porous structure [15]. Due to the hydrolysis of TEOS, the
2.3.6. Permeation property measurements
The permeation flux and rejection of the membranes were mea-
sured by UF experimental equipment, as described by Lang et al.
[15]. The rejection test was carried out with an aqueous solution
of BSA (300 mg L−1 ). All experiments were conducted at 25 ◦ C and
under the feed pressure of 0.1 MPa. The newly prepared hollow fiber
membranes were pre-pressured at 0.1 MPa using the pure water for
1 h before measurement, then the pure water permeation (Jw ) was
measured, finally the permeation flux (JBSA ) and rejection (R) for
the BSA solution were measured. The concentrations of BSA in the
permeate and feed were determined by an UV-spectrophotometer
(Shimadzu UV-3000, Japan). The permeation flux (J) and rejection
(R) were defined as formulae (4) and (5), respectively [15].
Q
J= (4)
A×T
 CP

R= 1− × 100% (5)
CF
where J was the permeation flux of membrane for pure water or BSA
solution (L h−1 m−2 ), Q was the volume of the permeate pure water
or BSA solution (L), A was the effective area of the membrane (m2 )
and T was the permeation time (h). R was the rejection to BSA (%), Fig. 2. Effect of TEOS concentration on the viscosity of PVDF dopes.
260 L.-Y. Yu et al. / Journal of Membrane Science 337 (2009) 257–265
Fig. 3. Effect of TEOS concentration in PVDF dopes on precipitation kinetics (using
pure water as coagulation fluid at room temperature).
resulting hydrophilic SiO2 absorbed water quickly than hydropho-
bic PVDF, which promoted the demixing process of the system. On
the other side, precipitation rate was also related to the dope vis-
cosity [36]. A higher viscosity would decrease the precipitation rate
of the dopes. The addition of SiO2 sol increased the dope viscosity
at higher concentration as shown in Fig. 2. That was not favorable
for the diffusion of water and solvent, resulted in a decrease of the
precipitation rate. The final behavior of PVDF–SiO2 dope depended
on the comprehensive result of two effects. Therefore, the precip-
itation rate decreased when the TEOS concentration in dope was
higher than 3 wt.% (MTEOS-4 and MTEOS-5).
3.2. Morphologies of membranes
The cross-section morphologies of PVDF and PVDF–SiO2 mem-
branes were shown in Fig. 4. With the increase of TEOS
concentration, a typical transition from asymmetric structure
to microcellular structure could be observed in membrane
cross-section. The topical asymmetric structure of membrane
cross-section (MTEOS-0, MTEOS-1 and MTEOS-2) became faint and
Fig. 4. Cross-section morphologies of MTEOS-0 to MTEOS-5 (magnification 300×).
the structure of sublayer underwent a transition from finger-like to
sponge-like structure (MTEOS-3, MTEOS-4 and MTEOS-5). More-
over, no aggregation of SiO2 particles was observed, which meant
that SiO2 was homogeneously dispersed in PVDF matrix. The reason
could be the formation of a crosslinking structure of SiO2 particles
with polymeric chains after the sol–gel process, which restrict-
ing the growth of the finger-like cavities. Moreover, the increase
in the dope viscosity due to the addition of SiO2 sol (as seen in
Fig. 2) hindered the demixing process, resulting in the suppression
of macrovoids [8].
The morphologies for internal and external surfaces of the PVDF
membranes with and without SiO2 were shown in Figs. 5 and 6.
The lower amount of added TEOS (≤3 wt.%) resulted in the increase
of surface pores compared with PVDF membrane (MTEOS-0). This
phenomenon could be interpreted as follows: the precipitation rate
increased with increasing TEOS concentration from MTEOS-0 to
MTEOS-3 (as shown in Fig. 3), which favored the formation of a
porous structure. However, higher TEOS concentration increased
the dope viscosity (as seen in Fig. 2), thereby slowing down the
precipitation rate and leading to a denser surface (such as MTEOS-4
and MTEOS-5 in Figs. 5 and 6).
EDX map scanning spectra in Fig. 7 showed the disper-
sion–aggregation phenomenon of silica on the external surface of
PVDF–SiO2 hollow fiber membrane made from MTEOS-3. The dif-
ferent color spots over the dark background indicated the location
of the relative elements on the external surface of composite mem-
brane. Red, green and blue spots in Fig. 7 corresponded to carbon
(C), fluorin (F) and silicon (Si), respectively. The EDX spectra showed
almost uniform distribution of silicon, which indicated better dis-
persion of silica in PVDF–SiO2 hollow fiber membrane made from
MTEOS-3.
3.3. Mechanical properties and thermal stability of membranes
The results of mechanical strength test including break strength
and Young’s modulus were listed in Table 1. It was clear that the
mechanical strength of membranes enhanced with the increase
of inorganic content, especially, at 3 wt.% TEOS concentration,
the break strength and Young’s modulus reached the peak value,
respectively, and then declined with the further increase of TEOS
concentration. At higher TEOS concentration, the formed SiO2 net-
work increased the rigidness of membrane [37] and confined the
crystallization of PVDF (which would be discussed later), this finally
 L.-Y. Yu et al. / Journal of Membrane Science 337 (2009) 257–265 261

Fig. 5. Internal surface morphologies of MTEOS-0 to MTEOS-5 (magnification 20,000×).

Fig. 6. External surface morphologies of MTEOS-0 to MTEOS-5 (magnification 20,000×).

led to the decrease of the mechanical properties, such as elongation polymeric matrix and led to looser structure in cross-section. The
at break. SEM images indicated that the addition of TEOS greatly influenced
Fig. 8 shows the magnification of sublayer membranes with dif- the membrane structures, thereby altering the mechanical prop-
ferent TEOS concentrations. All the membranes had a sponge-like erties of composite membranes. There were interactions between
cross-section but also presented some differences in compact mor- SiO2 and PVDF. SiO2 could act as a crosslinking point in composite
phologies. For the pure PVDF membrane, cellular pores formed in membranes to link the polymeric chains [22] and increase the rigid-
the cross-section. When the TEOS addition amount was 3 wt.%, the ity of polymeric chains. So more energy was needed to break down
cross-section became a little denser. While with the TEOS concen- the bond between SiO2 and PVDF, and the mechanical strength of
tration increasing to 5 wt.%, there were some massive aggregates in composite membranes was improved.
As shown in Fig. 9, the higher thermal decomposition temper-
Table 1
ature Td (defined as the temperature at 3% weight loss) for the
Mechanical properties of PVDF–SiO2 hollow fiber membranes. PVDF–SiO2 composite membranes, compared with that of the pure
PVDF membrane, indicated a better thermal stability of the com-
Membrane no. Break strength Young’s modulus Elongation at
posite membranes, probably because of the interactions between
(MPa) (MPa) break (%)
PVDF chains and SiO2 surface groups.
MTEOS-0 1.61 5.75 257
MTEOS-1 1.90 8.50 189
MTEOS-2 2.21 10.4 181 3.4. Crystalline structure of membranes
MTEOS-3 2.39 11.3 160
MTEOS-4 2.10 9.43 86.8 PVDF could crystallize in four different polymorphs (␣, ␤, ␥,
MTEOS-5 1.73 7.33 73.9
and ␦), and each crystal structure had different polymorphs [38].
262 L.-Y. Yu et al. / Journal of Membrane Science 337 (2009) 257–265

Fig. 7. EDX map scanning spectra for the external surface of MTEOS-3.

Fig. 8. Sublayer morphologies of MTEOS-0, MTEOS-3 and MTEOS-5 (magnification 10,000×).

Here crystalline phases of PVDF membranes were investigated by
XRD and FTIR spectroscopy. Fig. 10 shows the XRD patterns of
PVDF membranes with and without SiO2 . The diffraction peaks at
2 = 18.4◦ , 20.0◦ and 26.6◦ assigned to ␣(0 1 0), ␣(1 1 0), and ␣(0 2 1),
respectively, were the characteristic of the ␣-phase crystal struc-
ture [38]. This meant that pure PVDF membrane contained mainly
␣-crystal. With the addition of TEOS, a new peak at 2 = 20.78◦
appeared, which was assigned to ␤(1 1 0) and ␤(2 0 0) planes [39].
In particular, the strongest diffraction peak at 2 = 20.78◦ occurred
in MTEOS-3, which indicated the maximum percent ␤ PVDF crys-
tallinity. The generated SiO2 changed the PVDF crystal formation
during the phase inversion process, from the ␣-crystal structure to
the ␤ one. The proportion of the latter went through a maximum at

Fig. 9. TGA curves of PVDF–SiO2 membranes: MTEOS-0, Td 428.12 ◦ C; MTEOS-1, Td

446.41 ◦ C; MTEOS-2, Td 450.99 ◦ C; MTEOS-3, Td 458.46 ◦ C; MTEOS-4, Td 455.73 ◦ C; Fig. 10. XRD patterns of PVDF and PVDF–SiO2 membranes with different TEOS con-
MTEOS-5 Td 448.82 ◦ C. centrations.
 L.-Y. Yu et al. / Journal of Membrane Science 337 (2009) 257–265 263

Table 3
Contact angle and pore structure parameters of PVDF–SiO2 membranes with differ-
ent TEOS concentrations.

Membrane TEOS concentration Contact Porosity Pore size

no. (wt.%) angle  (◦ ) ε (%)
rm (␮m) rmax (␮m)

MTEOS-0 0 82.9 52.5 0.074 0.18

MTEOS-1 1 78.5 70.2 0.089 0.24
MTEOS-2 2 64.4 76.5 0.096 0.44
MTEOS-3 3 53.4 84.2 0.099 0.54
MTEOS-4 4 67.7 66.5 0.095 0.42
MTEOS-5 5 76.3 61.4 0.082 0.31

The porosity and pore size information of the prepared mem-

branes were listed in Table 3. It was shown that the porosity (ε),
mean pore size (rm ) and maximum pore size (rmax ) increased for
PVDF–SiO2 membranes with lower SiO2 amount. When the TEOS
concentration in dope at higher filling amount (>3 wt.%), the result-
ing PVDF–SiO2 membranes got smaller ε, rm and rmax . If PVDF
Fig. 11. FTIR spectra of (a) SiO2 prepared by sol–gel method, (b) PVDF membrane
and SiO2 were miscible, a stronger repulse force existed which led
and (c) PVDF–SiO2 membrane made from MTEOS-3.
to a stronger interfacial stress between polymer and SiO2 parti-
cles, because PVDF was hydrophobic and SiO2 was hydrophilic, and
3 wt.% of TEOS. This change was attributed to the PVDF chain con- finally formed interfacial pores due to the shrinkage of organic
finement by the SiO2 network. As reported in literature [40], only a phase during the demixing process [17]. However, if TEOS pro-
small amount of SiO2 networks led to the increase of polymer crys- duced a network structure of SiO2 which confined the movement
tallinity in crystalline polymer blends or composites; while beyond of PVDF chains [22], and at higher TEOS loading the condensation
a certain amount of SiO2 , the crystallization of PVDF was confined, reaction induced the formation of denser structure, consequently
similar to poly(ethylene oxide)–SiO2 hybrids [40]. suppressed defects in the membranes.
Fig. 11 shows the FTIR spectra of SiO2 , PVDF membrane and
PVDF–SiO2 composite membrane made from MTEOS-3. And the
3.6. Permeation and antifouling properties of membranes
wavenumbers of the FTIR peaks assigned to different groups and
crystallites were exhibited in Table 2, from which the main conclu-
The influences of TEOS concentration on permeability and
sions would be: (i) confirmation of the crystalline structures given
rejection were investigated through UF experiments. In Fig. 12, the
by XRD, and (ii) the increase in formed –OH groups with the TEOS
PVDF–SiO2 composite membrane permeability increased firstly
content.
and then decreased with the increase of SiO2 amount, a maximum
value 301 L h−1 m−2 of pure water and 255 L h−1 m−2 of BSA solu-
3.5. Hydrophilicity, porosity and pore size of membranes
tion presented for membrane prepared from the dope with 3 wt.%
TEOS concentration. The increase of the membrane hydrophilicity
The surface hydrophilicity of membranes could affect the flux
and pore size with lower TEOS concentration (≤3 wt.%) in Table 3
and antifouling ability of membranes. In general, the hydrophilic-
could attract water molecules inside the membrane matrix and
ity was evaluated by water contact angle, and higher hydrophilicity
promote them to pass through the membrane and accordingly
smaller contact angle [17]. The contact angle data of PVDF–SiO2
enhance the permeability. However higher TEOS concentration
composite membranes were shown in Table 3. The surface
(>3 wt.%) formed a highly viscous dope, which slowed down the
hydrophilicity was improved with the SiO2 amount in membrane.
formation process of PVDF–SiO2 composite membranes. The for-
As revealed by FTIR spectra, large amount of –OH groups on the SiO2
mation of SiO2 network compressed the movement of PVDF chains,
particles generated by TEOS hydrolysis were responsible for the
hydrophilicity increasing [8]. However, the contact angle of com-
posite membranes increased when TEOS concentration was higher
than 3 wt.%. The reason could be the formation of large scale SiO2
network at higher TEOS content, which consumed –OH groups due
to the condensation reaction between Si–OH. While at lower TEOS
concentration, SiO2 could be dispersed as smaller particles in PVDF
matrix and increased the amount of –OH groups.

Table 2
FTIR peak assignments for (a) SiO2 prepared by sol–gel method, (b) PVDF membrane
and (c) PVDF–SiO2 membrane made from MTEOS-3.

Wavenumbers (cm−1 ) Functional groups and crystallites

3500–3000 –OH stretching

2960 C–H stretching
1629 H–O–H bending
1378 C–H deformation
1230, 1155 C–F stretching
1220, 1080 Asymmetric Si–O–Si stretching
957 Si–OH stretching
800 Symmetric Si–O–Si stretching
976, 855, 766, 612, 531 ␣-Crystal of PVDF
840, 470 ␤-Crystal of PVDF Fig. 12. Curves of Jw and JBSA , rejection (R) and the ratio (JBSA /Jw ) of PVDF–SiO2
membranes as a function of TEOS concentration.
264 L.-Y. Yu et al. / Journal of Membrane Science 337 (2009) 257–265
Fig. 13. AFM three-dimensional external surface images of membranes: (a) MTEOS-0 and (b) MTEOS-3.
hindered the formation of macrovoid structure and decreased the
pose size (as shown in Figs. 4–6). Moreover, the condensation
of SiO2 into network consumed its surface –OH and decreased
the hydrophilicity, resulting in the decrease of the permeability.
Furthermore, the rejection changed slightly with the increase of
TEOS concentration and had a minimum at 3 wt.% TEOS. This result
could be explained by the fact that the increase of pore size had
a negative effect on rejection when TEOS concentration under
3 wt.%. However, at higher concentration (>3 wt.%), the formation
of denser structure resulted in the increase of rejection.
Besides, the antifouling properties of PVDF–SiO2 composite hol-
low fiber UF membranes could be evaluated by the ratio of BSA
solution flux (JBSA ) and pure water flux (Jw ). For the higher antifoul-
ing UF membrane, the addition of BSA in the feed solution would
cause a little flux loss and the ratio (JBSA /Jw ) would be higher [15].
As shown in Fig. 12, the ratio (JBSA /Jw ) increased firstly and then
decreased slightly for PVDF–SiO2 composite membrane prepared
from the dope with the increase of TEOS concentration.
Fig. 13 displayed three-dimensional AFM images of the mem-
brane external surfaces. The surface roughness of PVDF–SiO2
composite membrane made from MTEOS-3 was apparently higher
than that of the PVDF membrane. In the range of the scan area
10 ␮m × 10 ␮m, the Ra of the MTEOS-0 and MTEOS-3 membranes
were 19.2 and 30.1 nm, respectively. Higher roughness might relate
to the higher porosity of the external surface of membrane as
seen in Fig. 6, which could lead to two changes in the compos-
ite membranes: one was an increase of efficient filtration area and
another was a decrease of the antifouling performance [16]. Cer-
tain amount of hydroxyl groups on the hydrophilic SiO2 particles
[41] was beneficial to the membrane permeation. The enlarged
efficient membrane area would increase the membrane flux. The
membrane-fouling trend increased with roughness owing to con-
taminants accumulating in the “valleys” of the rough membrane
surfaces [16]. Since the introduction of SiO2 particles increased
the hydrophilicity of the membrane surface and pore walls, the
adsorbed foulants on the PVDF–SiO2 composite membranes could
be more readily dislodged by shear force than those on the pure
PVDF membrane, and thus improving the antifouling performance
of membrane.
4. Conclusions
Organic–inorganic PVDF–SiO2 composite hollow fiber UF mem-
branes were synthesized using the sol–gel and wet-spinning
process. The microstructure, mechanical property and thermal sta-
bility, hydrophilicity, permeation and antifouling performance of
composite membranes were improved apparently by an appropri-
ate choice of TEOS concentration. The main conclusions were listed
as follows:
(1) The dope viscosity increased with the increase of TEOS concen-
tration. The addition of TEOS accelerated the demixing process,
in particular, the precipitation rate reached the highest at 3 wt.%
TEOS in dope.
(2) Macrovoids were restricted or eliminated with the formation of
a sponge-like cross-section. The membranes with different sur-
face morphology were produced due to the effect of inorganic
particles on the dope viscosity and the precipitation rate. The
SiO2 particles distributed uniformly in the membrane matrix at
3 wt.% TEOS.
(3) Mechanical property, thermal stability, XRD and FTIR analy-
ses indicated that there was a crosslinking structure between
inorganic network and polymeric chains, which led to the
improvement of mechanical and thermal properties. Crys-
talline analysis results showed that the composite membranes
possessed predominantly PVDF ␤-phase while the polymeric
membrane presented mainly PVDF ␣-phase, especially the
maximum percent crystallinity of PVDF occurred at the content
of 3 wt.% TEOS.
(4) The presence of SiO2 particles generated by TEOS hydrolysis
containing an amount of hydroxyl groups, responsible for the
hydrophilicity increase of the composite membranes. At the
same time, the improvement of membrane hydrophilicity also
enhanced both the permeability and antifouling performance.
Particularly, the composite membrane with the maximum flux
and highest pollution resistance was obtained when TEOS was
3 wt.%, which was attributed to the maximum pore size of sur-
face as well as the increase of the membrane’s porosity and
hydrophilicity at 3 wt.% TEOS concentration.
Acknowledgement
The authors acknowledge the National Key Fundamental
Research Development Plan (“973” Plan, No. 2003CB615705) for
giving financial supports in this project.
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