Journal of Membrane Science 363 (2010) 128–139

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Journal of Membrane Science

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Hybrid anion exchange hollow fiber membranes through sol–gel process of

different organic silanes within BPPO matrix
Na Wang a , Cuiming Wu b , Yonghui Wu a , Tongwen Xu a,∗
a
Lab of Functional Membranes, School of Chemistry and Material Science, University of Science and Technology of China, Hefei 230026, PR China
b
School of Chemical Engineering, Hefei University of Technology, Hefei 230009, PR China

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

Article history: A series of hybrid anion exchange hollow fiber membranes have been prepared through modification of
Received 26 July 2009 brominated poly (2,6-dimethyl-1,4-phenylene oxide) (BPPO), sol–gel process of different organic silanes
Received in revised form 6 July 2010 and quaternization with triethylamino (TEA). Five different silanes are used, including tetraethoxysi-
Accepted 13 July 2010
lane (TEOS), ␥-(2,3-epoxy propoxy)propyl-trimethoxylsilane (GPTMS), ␥-aminopropyl triethoxysilane
Available online 27 July 2010
(␥-APS), phenyl-triethoxylsilane (EPh) and ␥-methacryloxypropyl trimethoxysilane (␥-MPS). Membrane
properties are characterized to show that the hybrid membranes generally exhibit improved thermal sta-
Keywords:
bility, mechanical stability and dimensional stability as compared with the membranes without organic
Hybrid membrane
Anion exchange membrane
silane treatment. Besides, the content and category of the silanes also influence membrane character-
Hollow fiber membrane izations such as ion exchange capacity (IEC), water content (WR ) and dimensional stability. TEOS, EPh
BPPO and ␥-MPS are recommended and the hybrid membranes from them demonstrate IEC in the range of
Protein adsorption and desorption 1.69–1.76 mmol/g, WR 63–72% and dimensional change ratio (DCR) 13–18%. For the recommended mem-
branes, their static and dynamic adsorption and desorption behaviors of a model protein (bovine serum
albumin, BSA) have been studied. Results show that the hybrid membranes can demonstrate excellent
performance during the adsorption–washing–elution procedures in the permeation mode and the elution
percentage can reach ∼95%.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction
During the last 50 years, ion exchange membranes have evolved
from a laboratory tool to industrial products with significant tech-
nical and commercial impact [1]. According to the physical shape,
ion exchange membranes can be classified into flat sheet and hol-
low fiber membranes. Though flat sheet membranes have been
earlier and more extensively researched and used, hollow fiber
membranes exhibit unique advantages during the preparation and
application processes [2]. For instance, ion exchange hollow fibers
can be self-supporting without separators, gaskets, reinforcing
plates, clamping plates, etc. Besides, fibers can be easily trans-
formed into different forms of modules to meet the application
demands. Hence, the weight and cost of equipments can be greatly
reduced and the operation more convenient. Furthermore, hollow
fibers have larger effective mass transfer area and high flux. There-
fore, they are more efficient than flat sheet membranes for the
separation or absorption process [2,3].
Because of the merits as listed above, ion exchange hollow fiber
membranes have attracted the attention of many researches dur-
∗ Corresponding author. Tel.: +86 05513601587; fax: +86 05513601592.
E-mail address: twxu@ustc.edu.cn (T. Xu).
ing the recent years. They are investigated for potential use in the
fields of chemical, environmental and biomedical industries, such
as purification of proteins and aminophenols [4–8], treatment of
waste water and reclaim of metals [9–11], purification of drinking
water [12,13], reclaim or separation of organic solvents [14], gases
separation [15–17] and so on.
For preparation of ion exchange hollow fiber membranes,
polysulfone (PSf), polyethersulfone (PES), polypropylene (PP), poly-
acrylonitrile (PAN) and polyvinyl alcohol (PVA), etc. [2] have been
commonly used. Due to the inherent limit of these polymer mate-
rials in chemical stability, harsh operation conditions should be
avoided and thus application under severe conditions such as
high temperature, strongly oxidizing conditions or organic solvents
cannot be achieved. Furthermore, since the hollow fiber mem-
branes need to be self-supported with no reinforcing materials,
improvement of the mechanical strength of conventional mem-
brane materials is another concern. For example, anion exchange
membranes, especially those prepared by quaternization, generally
show poor mechanical stability when the ion exchange capacity
(IEC) values are high [18].
For enhancement of the membranes chemical and mechani-
cal properties, different modification methods can be applied. For
instance, cross-linking [18] and heat-treatment [19] have been
tried and proven effective for flat sheet membranes. Another novel

0376-7388/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2010.07.020
 N. Wang et al. / Journal of Membrane Science 363 (2010) 128–139
Fig. 1. Chemical structures of the organic silanes: TEOS, GPTMS, ␥-APS, EPh and ␥-MPS.
method for modification can also be considered: the incorpora-
tion of inorganic component to form organic–inorganic membrane
materials. As a new kind of materials developed from 1980s,
organic–inorganic materials can combine the remarkable features
of inorganic materials with those of organic materials [20–24].
Therefore, the incorporation of inorganic oxides, such as SiO2 and
TiO2 , can significantly improve the stability and strength of the
polymer membranes.
Up to now, flat sheet organic-inorganic ion exchange mem-
branes have been widely explored. For example, silica-Nafion,
silica-sulfonated poly (ether ether ketone) (SPEEK), silica-
poly(vinyl alcohol) (PVA) or brominated poly(2,6-dimethyl-1,4-
phenylene oxide) (BPPO) ion exchange membranes have been pre-
pared from the sol–gel reaction of organic silanes in presence of the
polymers [25–28]. Unfortunately, little work has been conducted
for organic–inorganic ion exchange hollow fiber membranes.
Accordingly, previously in our laboratory, BPPO hollow
fiber membranes were modified through sol–gel reaction of
tetraethoxysilane (TEOS) [29]. The obtained hybrid anion exchange
membranes possess both higher thermal stability and dimen-
sional stability than BPPO membranes without hybrid process
[29,30]. The present work is an extended effort of ours for
exploration of hybrid anion exchange hollow fiber membranes
based on BPPO. As the category of the organic silanes can play
a significant role in the properties of the membranes, here we
choose five kinds of organic silanes including tetraethoxysilane
(TEOS), ␥-(2,3-epoxy propoxy)propyl-trimethoxylsilane (GPTMS),
␥-aminopropyl triethoxysilane (␥-APS), phenyl-triethoxylsilane
(EPh) and ␥-methacryloxypropyl trimethoxysilane (␥-MPS). The
chemical structures of the silanes, as shown in Fig. 1, are highly
diverse: TEOS has four alkoxy groups while the others have three;
EPh has a phenyl group which is hydrophobic and ␥-APS has a
hydrophilic amino group; the epoxy or methacrylate group in
GPTMS or ␥-MPS is active and can be easily further modified
through ring-opening or polymerization processes [31,32]. Thus,
the membranes modified with these silanes are expected to possess
different properties in hydrophilicity, functionality, stability, etc.
Characterizations concerning the membranes structure and mor-
phology, thermal stability, mechanical stability, charged property,
hydrophilicity, dimensional stability will be fully carried out and
the impacts of the different silanes will be discussed and com-
pared. The membranes with best performances will be chosen and
characterized further for protein adsorption and desorption prop-
erties. Bovine serum albumin (BSA), as a model protein, will be
used for the static adsorption and desorption experiments, and
adsorption–washing–elution experiments on permeation mode.
2. Experimental
2.1. Materials
Brominated PPO (BPPO) with 90% benzyl substitution and
10% aryl substitution was kindly supplied by Tianwei Membrane
129
Corporation Ltd. of Shandong (China). BSA was purchased from
Sinonpharm Chemical Reagent Corporation Ltd. (China) and pre-
served at 0–4 ◦ C until it was used. The other reagents were all of
analytical grade and commercially obtained from domestic chemi-
cal reagents companies. Deionized water was used throughout. The
silanes including TEOS, EPh, GPTMS, ␥-APS, and ␥-MPS were diluted
with ethanol to 1.0 mol/l before use.
2.2. Preparation of hybrid anion exchange hollow fiber
membranes
Base BPPO hollow fiber membranes were prepared in an indus-
trial spinning line, which contained dissolution, filtration, spinning,
coagulation, and take-up units. Preparation conditions have been
described in detail in our previous paper [30]. The obtained
hollow fiber membranes have an outer diameter of 1.30 mm
and a thickness of 0.27 mm (in dry state), with a porosity of
∼70%.
The preparation of hybrid anion exchange membranes generally
followed similar procedures as our previous work [29]. However,
some modifications were conducted for improving the membrane
properties, as summarized in the following:
(1) Step 1: pretreatment. The BPPO hollow fiber membranes were
immersed in 1.0 mol/l KOH aqueous solution at 60 ◦ C for 24 h.
After that, the membranes were dried at 45 ◦ C for 6 h. The prod-
uct was denoted as BPPO-OH. This step of pretreatment has not
been included in our previous work [29]. Here it was applied to
generate the benzyl-OH groups on BPPO chains, which can take
part in the following sol–gel process to form –C–O–Si– bonding
[33].
(2) Step 2: sol–gel process. The pretreated BPPO-OH membranes
were kept for 12 h in the different silane/ethanol solutions
(1.0 mol/l) at room temperature. Afterwards, 0.02 mol/l HCl was
added into silane/ethanol and mixed to form a homogeneous
solution. The membranes were maintained in the solution for
3 h, then taken out, washed and dried at 45 ◦ C for 6 h. Note that
the drying temperature here was much lower than that in our
previous membranes (70 ◦ C for 2 h and 90 ◦ C for 2 h), so as to
decrease the membrane brittleness. Molar ratio of Si to water in
HCl solution was controlled to be 1:6. The product of this step
was denoted as BPPO-SiO2 .
(3) Step 3: quaternization. BPPO-SiO2 membranes from step 2 were
kept in 1.0 mol/l triethylamine (TEA)/ethanol solution for 6 h at
room temperature. After washing with ethanol and deionized
water repeatedly, the membranes were air-dried at room tem-
perature for 12 h and then at 45 ◦ C for 6 h. Note that TEA was
used here in place of trimethylamine (TMA) previously [29].
Besides, the quaternization time was shortened (previously
24 h). The obtained fiber membranes were denoted in general as
BPPO-SiO2 (+). To distinguish the membranes from the different
silanes, membranes from TEOS, EPh, GPTMS, ␥-APS and ␥-MPS
130 N. Wang et al. / Journal of Membrane Science 363 (2010) 128–139
Scheme 1. The preparation procedures of hollow fiber anion exchange hybrid membranes from bromomethylated poly(2,6-dimethyl-1,4-phenylene oxide) (BPPO); “R”
denotes the different organic groups from the silanes.
were signified as BPPO-TEOS(+), BPPO-EPh(+), BPPO-GPTMS(+),
BPPO-␥-APS(+) and BPPO-␥-MPS(+) respectively.
The above three steps were illustrated in Scheme 1. For com-
parison, a group of BPPO base fiber membranes were conducted
only by the pretreatment and quaternization processes (steps 1 and
3), without sol-gel process with the silanes (step 2). The prepared
membranes were thus denoted as BPPO(+).
2.3. Characterization of the hybrid anion exchange hollow fiber
membranes
2.3.1. Chemical structure, thermal stability and morphology
To investigate the chemical structure of the hollow fiber mem-
branes, FTIR spectra were recorded using FTIR spectrometer (Vector
22, Bruker) with a resolution of 2 cm−1 and a spectral range of
4000–400 cm−1 . The thermal behavior was analyzed with a Shi-
madzu TGA-50H analyzer under air flow and with a heating rate
of 10 ◦ C/min. A scanning electron microscopy (XT30 ESEM-TMP
PHILIP) was used to observe the cross-section morphologies of the
different fiber membranes. The samples were fractured in liquid N2
and coated with gold before the observation.
2.3.2. Ion exchange capacity (IEC)
The ion exchange capacity (IEC) was determined by the Mohr
method. BPPO-SiO2 (+) fiber membranes was transformed to chlo-
ride (Cl− ) form first, then converted to sulfate (SO4 2− ) form by
immersing in 0.5 mol/l Na2 SO4 solution. The chloride ions released
from the membranes were determined by titration with 0.1 mol/l
AgNO3 solution using K2 CrO4 as indicator. IECs were calculated
with the following equation:
VAg × CAg
IEC = (mmol/g dry membrane in Cl− form)
W mined by measuring the UV absorbance at 279 nm throughout the
where VAg and CAg are respectively the volume and concentration
of AgNO3 solution. W is the weight of the dry membranes in Cl−
form.
2.3.3. Water content (WR ) and dimensional stability in water
For measurement of WR , BPPO-SiO2 (+) and BPPO(+) membrane
samples were kept in water for 2 days. Then they were cut into
halves along the longitudinal direction, carefully removed the sur-
face water and weighed. Afterwards, the samples were dried at
45 ◦ C for 6 h. WR was calculated as the relative weight gain per
gram of the dry samples.
Dimensional stability is indicated by the dimensional change
ratio (DCR), which is determined by the following equation:
L2 − L1
DCR (%) = × 100 (2)
L1
where L1 and L2 are the length of the fiber samples in dry and wet
state, respectively.
2.3.4. Mechanical strength
For the mechanical strength test, the BPPO base fiber membrane,
BPPO(+) and BPPO-SiO2 (+) membranes were immersed in water for
more than 12 h. Then they were taken out and measured using an
Instron universal tester (Model 1185) at 25 ◦ C. The crosshead speed
during elongation was 25 mm/min, while the initial gauge length
was set as 20 mm. Tensile strength (TS) and elongation at break (Eb)
values were recorded.
2.4. BSA adsorption and desorption behaviors
2.4.1. Static adsorption and desorption of BSA
The static adsorption experiments were performed in 2.0 mg/ml
BSA aqueous solution with pH 8.0 (adjusted by 0.02 mol/l Tris–HCl
buffer) for 24 h. The static desorption experiments were performed
by washing the BSA adsorbed membranes with 0.5 mol/l NaCl solu-
tion at varied pH (3.0, 5.0 and 8.0) for 6 times. The total medium
volume was 48 ml. The pH values of the eluents were adjusted
by disodium hydrogen phosphate–citric acid buffer (0.2 mol/l). All
these experiments were performed at room temperature and each
(1) time of desorption lasted for 12 h. The BSA concentration was deter-
static and the following dynamic experiments.
2.4.2. BSA adsorption and elution during the permeation mode
One 15-cm-long (wet length) BPPO-TEOS(+) membrane was
positioned in a U-shaped glass tube as shown in Fig. 2. Before the
adsorption procedure, 0.02 mol/l Tris–HCl buffer was forced to per-
meate through the membrane for 30 min. After that, BSA aqueous
 N. Wang et al. / Journal of Membrane Science 363 (2010) 128–139 131

Fig. 2. Experimental apparatus for dynamic adsorption, washing and elution of BSA through the pores of BPPO-TEOS(+) hollow fiber membrane.

solution (2.0 mg/ml, pH 8.0) as a feed was permeated radially at To investigate the content of the incorporated silanes, the
a constant rate of 1.0 ml/min. The effluent penetrating the outside weight gain (Wg ) of the hollow fiber membranes after the sol–gel
surface of the hollow fiber membrane was continuously collected process has been calculated with the following equation:
with fraction tubes. The equilibrium binding capacity (EBC) of the
W2 − W1
membrane for BSA in equilibrium with the feed concentration was Wg (%) = × 100 (5)
W1
calculated by the reported equation [31]:
 Ve in which W1 and W2 are the weight of the membranes in dry state
(C0 − C) dV before and after sol–gel process respectively. Wg values can indicate
EBC(mg − BSA/g) = (3)
0
WT the modification degree of the membranes with silica component
and will be related with the other properties of the membranes
where C0 and C are the concentrations of the feed and effluent,
such as IEC, WR , and so on.
respectively. V, Ve , and WT are the effluent volume, the effluent
The Wg results are shown in Fig. 3. It is observed that the Wg
volume at which C reached C0 , and the mass of the membrane in
values change much in the range of 8–22%. Molecular weights of
dry state, respectively.
the silanes are similar to each other (208–248 g/mol) and thus the
After the effluent concentration reached the feed concentration,
difference of Wg values should be ascribed to the difference of molar
the adsorption procedure was switched to washing and elution pro-
numbers of the incorporated silanes.
cedures. The washing liquid was 0.02 mol/l Tris–HCl buffer (pH 8.0)
Among the different silanes, membrane from TEOS (BPPO-
and the elution solution was 0.5 mol/l sodium chloride in disodium
TEOS(+)) shows the highest Wg value of 22%, indicating that TEOS
hydrogen phosphate–citric acid buffer (pH 5.0). For the washing
can be incorporated with the highest efficiency into the hollow
and the eluting processes, the permeation rate was both fixed at
fiber membranes. This should be ascribed to the highest function-
1.0 ml/min, while the lasting time was 9 min respectively. Elution
alization of TEOS, since TEOS molecules contain four alkoxy groups
percentage was defined as [31]
(–O–C2 H5 ), while the other silanes have only three. In our previ-
amount eluted ous work [29], the BPPO-TEOS(+) membrane has been prepared
Elution percentage (%) = 100 × (4)
amount bound
where “amount eluted” and “amount bound” were obtained by
integral calculus on BSA adsorption–washing–elution curve.

3. Results and discussion

3.1. Preliminary discussion on the membranes preparation

processes

As shown in Scheme 1, BPPO polymer chains contain benzyl

bromine groups (–CH2 Br) and can be easily transformed to qua-
ternary amine groups (–N+ Et3 ) through reaction with TEA (step 3
of Scheme 1) [34]. When different silanes have been used to mod-
ify the BPPO hollow fiber membranes, inorganic silica component
can be incorporated through sol-gel process of these silanes (step
2 of Scheme 1). The pretreatment with KOH solution (step 1) can
transform benzyl bromine (–CH2 Br) groups into benzyl hydroxyl
(–CH2 OH) groups, which can partially take part in the sol–gel pro-
cess and induce covalent crosslinkage between the BPPO polymer
chain with the silica network. Our previous work has shown that
Fig. 3. Weight gains (Wg ) of hollow fiber membranes after sol–gel process with
this step of pretreatment can increase the homogeneity of the different silanes. The names of silanes are used to represent the different membranes
BPPO-SiO2 hybrid membranes [33]. for short.
132 N. Wang et al. / Journal of Membrane Science 363 (2010) 128–139

Fig. 5. TGA thermograms of BPPO(+) and BPPO-SiO2 (+) hollow fiber membranes
treated with different silanes.

Fig. 4. FTIR spectra of BPPO base fiber membranes, BPPO(+) and BPPO-SiO2 (+) hol-
low fiber membranes treated with different silanes.
without the pretreatment step and its Wg value is much lower
(∼11%). This confirms again that the pretreatment is beneficial for
the incorporation of silica.
For EPh, ␥-MPS, GPTMS and ␥-APS, membrane from EPh (BPPO-
EPh(+)) shows the lowest Wg value, which should be due to the
high steric hindrance of EPh because of the presence of the phenyl
groups [35]. BPPO-␥-APS(+) and BPPO-GPTMS(+) membranes, on
the other hand, exhibit higher Wg value. The amino groups (–NH2 )
in ␥-APS or the epoxy groups in GPTMS can be crosslinked with
the BPPO polymer chains through reaction route (I) [36] or (II) [37].
Therefore, higher covalent linkage can be formed between the BPPO
polymer chain and the silica component when ␥-APS and GPTMS
are used, resulting into higher silica content incorporation.
R 1 -CH2 Br + H2 N-CH2 CH2 CH2 -R 2 → R 1 -CH2 CH2 CH2 CH2 -R 2 + HBr
(I)
1082 cm−1 (a(SiO–CO)) cm−1 and 968 cm−1 (ı(H3 CO), ı(H3 CC))
[38–40]. More careful observation demonstrates that the intensity
of the 1150–950 cm−1 band is higher for BPPO-TEOS(+) and BPPO-
␥-APS(+) curves than the other curves. This confirms the previous
result that the silica incorporation in these two membranes is the
highest.
3.3. Thermogravimetric analysis (TGA)
The thermal stability of BPPO-SiO2 (+) fiber membranes was
measured by means of TGA under air atmosphere and the obtained
diagrams are shown in Fig. 5. For comparison, the diagram of
BPPO(+) fiber is also illustrated. Weight loss before 90 ◦ C should be
caused by the loss of absorbed water and some remaining solvents
(such as ethanol) and thus will be neglected for the estimation of
the membranes thermal stability.
Through Fig. 5, the thermal degradation temperature (Td, tem-
perature at 5% weight loss) of the samples are collected and shown
in Fig. 6. BPPO-␥-APS(+) shows the lowest Td value of 178.5 ◦ C. This
indicates the lower thermal stability of BPPO-␥-APS(+), which may
result from the presence of relatively unstable amino groups in ␥-
APS molecules. Td value of BPPO-TEOS(+) membrane is 184.6 ◦ C, a

(II)

3.2. FTIR

To confirm the chemical structures, base BPPO membranes and

BPPO-SiO2 (+) membranes from the five silanes were characterized
with FTIR, as shown in Fig. 4. For comparison, FTIR spectrum of
BPPO(+) membrane without the sol–gel process is also shown.
Obviously, characteristic absorption bands from BPPO polymer
chains are observed at ∼1610, ∼1460, ∼1305 and ∼1192 cm−1
[18] in all the curves. Compared with the curve of BPPO, BPPO(+)
curve shows new broad band at ∼3450 cm−1 . This should be from
the–(CH2 )OH groups of BPPO(+), which have been formed dur-
ing the pretreatment process with KOH. For the five BPPO-SiO2 (+)
curves, the band at ∼3450 cm−1 is generally further strengthened
as compared with the BPPO(+) curve, because of the presence of
Si–OH groups. Besides, in the curves of BPPO-SiO2 (+) membranes,
the bands in the range of 1150–950 cm−1 also become broader
as compared with BPPO or BPPO(+) curves. This is due to the
Fig. 6. Td values of BPPO(+) and BPPO-SiO2 (+) hollow fiber membranes treated with
introduction of the characteristic peaks of the silanes, including different silanes. The names of silanes are used to represent the different membranes
1165 cm−1 (Si–O–C rocking), 1105 cm−1 (a(C–C + C–O), ı(COH)), for short.
 N. Wang et al. / Journal of Membrane Science 363 (2010) 128–139 133

Fig. 8. Ion exchange capacity (IEC) of BPPO-SiO2 (+) treated with different silanes.
Fig. 7. DrTGA thermograms of BPPO(+) and BPPO-SiO2 (+) hollow fiber membranes The names of silanes are used to represent the different membranes for short.
treated with different silanes.

polymer chains are better crosslinked with the silica component,

little lower than the value of our previous membrane (193 ◦ C) [29].
The difference can be readily understood, since the drying temper-
ature of our membranes is much lower (45 ◦ C for 6 h). However,
compared with BPPO(+) membrane (Td = 179.4 ◦ C), the Td values of
BPPO-TEOS(+), BPPO-EPh(+), BPPO-GPTMS(+) and BPPO-␥-MPS(+)
membranes (181.2–186.4 ◦ C) are all higher. Therefore, the incor-
poration of silica in BPPO fibers can increase the thermal stability,
which is in accordance with the result of our previous work [29].
Fig. 7 is the DrTGA curves of the BPPO(+) and BPPO-SiO2 (+) fiber
membranes. It can be seen that all the curves show five peaks. The
first peak before 120 ◦ C indicates the evaporation of the residual
solvent (ethanol) and water. And the second degradation of the
membranes around 200 ◦ C is due to the decomposition of the qua-
ternary ammonium groups [29]. The third and fourth degradation
in the range of 220–300 and 300–360 ◦ C are due to the decom-
position of some thermally unstable groups, for example, methyl
groups (–CH3 ), ethyl groups (–CH2 CH3 ) and ester groups from ␥-
MPS [34]. And the last degradation in the range of 465–590 ◦ C is
due to the formation of silica (SiO2 ) and the decomposition of the
carbon chain of copolymer and phenyl groups [34,41].
3.4. Ion exchange capacity (IEC)
leading to more compact membrane structure. Meanwhile, con-
tent of benzyl bromine (–CH2 Br) groups in BPPO is also decreased,
resulting into a lower quanternization degree. The above two fac-
tors are responsible for the lowest IEC value of BPPO-␥-APS(+)
membrane. Crosslinkage of GPTMS with BPPO can also take place,
as discussed in Section 3.1. However, the reaction of GPTMS with
BPPO does not consume the –CH2 Br groups and hence the IEC value
of BPPO-GPTMS(+) is higher than BPPO-␥-APS(+).
3.5. Water content (WR ) and dimensional change ratio (DCR)
Fig. 9 shows the values of WR and DCR of the different mem-
branes. WR , as a key factor in the ion and water transfer, is
mainly related with two factors: the degree of polymeric matrix
crosslinkage and the amount of hydrophilic or hydrophobic groups
[42]. In the membranes of our present work, the most impor-
tant hydrophilic group is quaternary ammonium group. Hence,
IEC value should be one of the mainly factors determining WR
value. Actually, the WR values in this work are relatively lower
(48.7–108%) than those of our previous membrane (108%) [29], due
to the relatively lower IEC.

Fig. 8 shows the IEC of the BPPO, BPPO(+) and BPPO-SiO2 (+)
membranes. As can be seen, the base BPPO membrane has no
obvious IEC value, while BPPO(+) membrane has the highest IEC
(1.87 mmol/g dry membrane). Lower IEC values of BPPO-SiO2 (+)
membrane (0.54–1.76 mmol/g dry membrane) than BPPO(+) is due
to the incorporation of non-charged silica component. Besides, sil-
ica network formation makes the membrane more compact and
thus will also decrease the membrane ion exchange ability.
Among the different BPPO-SiO2 (+) membranes, BPPO-TEOS(+),
BPPO-EPh(+) and BPPO-␥-MPS(+) show similar IEC values in the
range of 1.69–1.76 mmol/g dry membrane. These values are lower
than the value of our previous membrane (1.95 mmol/g) [29], which
should be due to the difference in the quaternization process: TEA
has been used in place of TMA and the quaternization time has also
been reduced. However, the IEC values here are relatively high as
compared to some reported values [8].
The IEC values of BPPO-␥-APS(+) and BPPO-GPTMS(+) mem-
branes are relatively lower (0.54 and 1.30 mmol/g dry membrane).
Fig. 9. Water content (WR ) and dimensional change ratio (DCR) of BPPO-SiO2 (+)
As discussed above, ␥-APS has –NH2 groups which can react with treated with different silanes. The names of silanes are used to represent the differ-
a portion of benzyl bromine groups of BPPO. Therefore, the BPPO ent membranes for short.
134 N. Wang et al. / Journal of Membrane Science 363 (2010) 128–139
Table 1
Elongation at break (Eb) and tensile strength (TS) of hybrid membranes treated with
different silanes.
Fiber membranes Eb (%)
BPPO 13.5
BPPO(+) 41.2
BPPO-EPh(+) 34.8
BPPO-␥-MPS(+) 16.8
BPPO-GPTMS(+) 21.9
BPPO-TEOS(+) 26.6
BPPO-␥-APS(+)a – –
a
BPPO-␥-APS(+) membrane was too brittle and could not be used for mechanical
properties measurement.
Among the different membranes, BPPO(+) membrane has high
content of quaternary ammonium groups, as reflected by its high-
est IEC value (Section 3.4) and therefore the WR value is high
(97.0%). Except BPPO-␥-APS(+), all the BPPO-SiO2 (+) membranes
show lower WR values (48.7–71.6%) than BPPO(+) membrane. This
is due to the lower content of quaternary ammonium groups and
the more compact structure of the BPPO-SiO2 (+) membranes. The
exceptionally high WR of BPPO-␥-APS(+) (108%) should be caused
by the presence of different amine groups: quaternary ammonium
groups (from quaternization process), secondary amines (from the
reaction route (1) in Section 3.1) and unreacted amino groups (from
the ␥-APS molecules). WR value of BPPO-EPh(+) is the lowest among
the different membranes, even lower than the base BPPO mem-
brane without any IEC value. This can be ascribed to the highly
hydrophobic phenyl groups from EPh. Summary of the different WR
values of the membranes indicates that membranes with greatly
changing hydrophility can be obtained through the change of the
silanes.
To some extent, DCR is the representation of WR in one
dimension of the membranes. But DCR depends on the degree
of cross-linkage to greater extent. Fig. 8 demonstrates that the
DCR values of BPPO-SiO2 (+) membranes are obviously lower than
that of BPPO(+). Hence, incorporation of silica can significantly
improve the membranes’ dimensional stability. For the different
BPPO-SiO2 (+) membranes, the DCR values follow the same trend
as WR , with the only exception of BPPO-␥-APS. The exceptionally
low DCR value of BPPO-␥-APS (1.24%) can be explained by the high
degree of cross-linkage between the organic and inorganic compo-
nents due to the reaction (1) presented in Section 3.1.
3.6. Mechanical properties
The membranes were tested in wet form for mechanical proper-
ties and the tensile strength (TS) and elongation at break (Eb) values
data are shown in Table 1. Membranes treated with ␥-APS are
quite brittle, which should be due to the crosslinking of ␥-APS with
BPPO. Hence BPPO-␥-APS(+) cannot be used for mechanical prop-
erties measurement and no data about BPPO-␥-APS(+) are shown
in Table 1.
Comparison of the Eb and TS values in Table 1 for the different
membranes shows the following points: 1) As compared with base
BPPO fiber membranes, BPPO(+) and BPPO-SiO2 (+) membranes
demonstrate higher Eb and lower TS. Therefore, quaternization
process can improve the membranes’ softness and tensibility but
decrease the tensile strength, very probably through the decrease
of the membranes compactness and enhancement of their IEC
and water content; 2) Among BPPO(+) and BPPO-SiO2 (+) mem-
branes, BPPO(+) shows the highest Eb (41.2%) and very low TS
(2.82MPa) values, indicating its high flexibility but poor strength.
BPPO-SiO2 (+) membranes, on the other hand, have generally lower
Eb value but higher TS, which is ascribed to their more compact
and brittle structure after the incorporation of silica component;
3) Among the different BPPO-SiO2 (+) membranes, regularity as
for the TS and Eb values is not always obvious. There are vari-
ous factors that may affect the mechanical performances of the
TS (MPa) membranes, such as the IEC value, the silica content, the water
7.81 content, crosslinking degree, length and category of the organic
2.82 groups in the silanes, etc. Therefore, changing trend of the TS
3.01 and Eb values is complicated. For example, Eb values of BPPO(+),
2.54
BPPO-EPh(+), BPPO-TEOS(+), BPPO-GPTMS(+) follow a gradually
4.61
2.82 decreasing trend, which is in accordance with the gradually
decreasing trend of their IEC values (Fig. 7). However, BPPO-
␥-MPS(+), who has highest IEC value among the BPPO-SiO2 (+)
membranes, exhibit lowest Eb and TS value. Other influencing fac-
tors than IEC, such as the long ester groups in ␥-MPS, the relatively
low WR value of BPPO-␥-MPS(+) should play the major role.
In our previous work [29], the mechanical strength of the BPPO-
TEOS(+) has not been examined. But general handling and visual
observation show that the present membranes are much more flex-
ible than the previous ones. The difference should be due to the
replacement of the quaternization agent (TEA in place of TMA) and
the decrease of heating temperatures. Therefore, modification of
the preparation procedures has proved to be effective in respect to
the membrane flexibility. High flexibility is vital to the actual appli-
cation of the membranes, such as in the field of proteins separation
and purification.
3.7. SEM
Microstructures of the cross section of the membranes are
observed through SEM. Before the observation, the membranes
have been fully wetted, then frozen in liquid Nitrogen so that the
morphology can be maintained.
As shown in Fig. 10, the base fiber (BPPO) exhibits a round
and plump shape and contains many finger-like macrovoids. The
macrovoids extent form the inner fiber surface to the middle of
the cross-section and their diameter can increase to a maximum
of 15–20 ␮m. Contrasted to the BPPO base fiber, the cross-section
of BPPO(+) changes into an asymmetric shape, indicating that the
membrane has been highly distorted. The finger-like structure
inside the fiber is also distorted and shrink to diameter of 5–10 ␮m.
Shrinkage of the macrovoids can be explained by the high swelling
property of BPPO(+) membrane, as reflected by its high WR and DCR
values (Section 3.5). Besides, the mechanical strength has also been
decreased, so that the wet fiber becomes flexible and can be more
easily distorted.
The micrographs of the five BPPO-SiO2 (+) membranes are
observed. And as typical representation, the microstructures of
BPPO-EPh(+) and BPPO-␥-MPS(+) are shown in Fig. 10. As can
be seen, the membranes remain the original round and plump
shape with much less distortion than BPPO(+) membranes. The
macrovoids show plumpness and regularity, with a diameter
of 6–10 ␮m. Therefore, incorporation of silica has increased the
mechanical stability of the membranes obviously, which confirms
the mechanical property testing results in the above section. More
careful observation shows that the graph of BPPO-EPh(+) mem-
brane at higher magnification shows a little distortion and swelling
in some area. For BPPO-␥-APS(+) membranes, no such distortion
can be observed. This result agrees well with the high dimensional
stability of BPPO-␥-APS(+), which is reflected by its low DCR value
(Section 3.5).
3.8. BSA adsorption and desorption behaviors
3.8.1. Static adsorption and desorption of BSA
As has been discussed in the above sections, BPPO-TEOS(+),
BPPO-EPh(+) and BPPO-␥-MPS(+) membranes show more excellent
properties in IEC (1.69–1.76 mmol/g dry membrane), WR (63–72%)
 N. Wang et al. / Journal of Membrane Science 363 (2010) 128–139
Fig. 10. SEM micrographs of the hollow fiber membranes.
and dimensional stability (DCR in the range of 13–18%). Therefore,
they are recommended for further applications. As an example,
their protein adsorption and desorption behaviors have been inves-
tigated with BSA as the model protein. The BPPO(+) membrane was
also observed for comparison.
Fig. 11(a) shows the static adsorption amount at pH 8.0 and des-
orption percentages at pH 3.0, 5.0, 8.0, respectively. Fig. 11(b)–(d)
show the specific desorption percentages of the membranes chang-
ing along with the eluent volume. It can be seen that the four
types of membranes show similar adsorption amount of BSA
(68.9–76.0 mg/g dry membrane). However, the desorption percent-
ages of the hybrid membranes are relatively lower than that of
BPPO(+). This is due to the existence of inorganic components,
which reduce the hydrophilicity of the hybrid membranes, and con-
sequently reduce the desorption percentage of the protein. And for
the same reason, the BPPO-TEOS(+) membrane, which has higher
hydrophilicity than BPPO-EPh(+) and BPPO-␥-MPS(+) membranes,
shows higher desorption percentage.
As for the effect of pH value during the desorption procedure,
the following points can be obtained from Fig. 11:
Generally, lower pH is advantageous to the desorption of BSA.
BSA, with the isoelectric point (IEP) at 4.8, is expected to switch
135
from electrically negative to nearly neutral, then to positive when
the pH value is reduced from 8.0, 5.0 to 3.0. Thereby the electro-
static attraction between the membrane and BSA molecules would
gradually decrease, leading to gradually higher desorption ratio.
The BPPO-TEOS(+) membrane abnormally shows lower des-
orption percentage at pH 3.0 (75.0%) than pH 5.0 (91.2%). This
phenomenon should be caused by the synergetic effect of the dif-
ferent interactions between the membrane and BSA molecules,
including electrostatic interactions and non-electrostatic interac-
tions (hydrogen bonding and hydrophobic interaction) [5]. In the
BPPO-TEOS(+) membrane, the amount of the alkoxy groups is the
highest. At low pH (pH 3.0), most of the silicon hydroxyl groups are
in the form of –SiOH, presenting large amount of proton donators
(–OH) to form hydrogen bonding with BSA. Hence the desorption
of BSA from the membranes is hampered.
Considering the good performance of the BPPO-TEOS(+) mem-
brane during static desorption procedure, it was chosen for
examination of the dynamic BSA adsorption and elution behaviors.
3.8.2. BSA adsorption and elution during the permeation mode
Fig. 12 shows the dynamic BSA adsorption-washing-elution
performance of the BPPO-TEOS(+) hollow fiber membrane. The x-
136 N. Wang et al. / Journal of Membrane Science 363 (2010) 128–139
Fig. 11. The static adsorption and desorption of BSA by BPPO(+), BPPO-EPh(+), BPPO-␥-MPS(+) and BPPO-TEOS(+) hollow fiber membranes, including the total BSA adsorption
amount at pH 8.0 and desporption percentages at varied pH values (a) and the specific desorption percentages changing along with the eluent volume at pH 3.0 (b), 5.0 (c)
and 8.0 (d).
coordinate is set as dimension-less effluent volume (DEV), which
is defined as effluent volume divided by the membrane volume
excluding the lumen. The equilibrium is reached at DEV of ∼43 with
BSA effluent concentration of 2.0 mg/ml. Therefore, nearly all BSA
Fig. 12. The dynamic adsorption-washing-elution of BSA through the BPPO-TEOS(+)
hollow fiber membrane at room temperature.
molecules can permeate through the membrane, indicating that
the molecular weight cut off (MWCO) of the membrane is higher
than 67 kDa.
More careful observation of Fig. 12 shows that there is a lit-
tle peak when the DEV is around 16. The effluent concentration
increases from DEV 0 to 16 (stage I in Fig. 12), then decreases from
DEV 16 to 31 (stage II) and then gradually increase (stage III) again.
Such peak has not been observed in other research reports [3,7].
For confirmation, repeat experiments have been conducted, and
similar results are obtained. Since the absorption and permeation
of the proteins in the membrane is quite complex, here only some
possible reasons can be presented:
The temporary blocking of the membrane pores. During the
early stage of BSA feeding, large number of BSA molecules adsorbed
on the interior surface of the membrane may block the pores (as
shown in Fig. 13(a)) and reduce the further permeation of BSA
(stage II in Fig. 12). As permeation proceeds, BSA accumulated at
the entrances of the pores may collapse under the feed force, caus-
ing further increase in the permeation amount (stage III in Fig. 12),
until the equilibrium is reached.
Concentration-dependent adsorption [43]. At the early stage of
BSA feeding, the concentration of BSA in the membrane is not a con-
stant but a variable increasing from 0 to 2.0 mg/ml. When the BSA
concentration is very low, the adsorption amount is small (illus-
trated in Fig. 13(b)). Thus the effluent concentration depends more
on the concentration inside the membrane, deducing a relatively
quick increase of the permeation amount with time (stage I in
 N. Wang et al. / Journal of Membrane Science 363 (2010) 128–139 137

Fig. 13. The proposed adsorption mechanism of BSA by BPPO-TEOS (+) hollow fiber membrane. (a) Increased hindrance at the membrane pore caused by the adsorbed BSA;
(b) and (c) Concentration-dependent adsorption of BSA by the membrane under low and high BSA concentration inside the membrane, respectively.

Fig. 12). However, when the BSA concentration inside the mem-
brane increases to some degree, the adsorption amount greatly
increases, including the adsorption in the pore and on the outer
surface of the membrane (shown in Fig. 13(c)). Hence, the effluent
concentration appears to decrease (stage II in Fig. 12).
The equilibrium binding capacity (EBC) for BSA in equilibrium
with the feed concentration was calculated by Eq. (3) from the
curve shown in Fig. 12. The calculated value of EBC is 69.9 mg/ml,
which is very close to the static adsorption amount (68.9 mg/ml).
And by integral operation of the elution peak in Fig. 12 and
then calculated by Eq. (4), we found the elution percentage of
BSA was 94.9%. This indicates that the BPPO-TEOS(+) membrane
has the potential to be applied on protein separation and puri-
fication.
138 N. Wang et al. / Journal of Membrane Science 363 (2010) 128–139
4. Conclusions
Five kinds of organic silanes, i.e. TEOS, GPTMS, ␥-APS, EPh and
␥-MPS, are used to modify BPPO base hollow fiber membranes.
Compared with BPPO(+) without silane treatment, most of the
hybrid membranes (BPPO-SiO2 (+)) show enhanced thermal sta-
bility, mechanical strength and dimensional stability because of
the incorporation of the silica content. The membrane from ␥-APS
(BPPO-␥-APS(+)) abnormally shows lower thermally degradation
temperature (Td ) and higher brittleness as the amino groups of
␥-APS are relatively thermally unstable and can react as a cross-
linking agent with BPPO.
The content and category of the silanes, including the number
of alkoxy groups, the steric hindrance and hydrophilic property
of the terminal groups, and their reactions with the BPPO mem-
brane matrix, play important role on the properties of the hybrid
membranes and cause the changes in ion exchange capacity (IEC),
water content (WR ), dimensional change ratio (DCR), and tensile
strength (TS). The membrane treated with TEOS, EPh and ␥-MPS
are recommended since they show more excellent properties in
IEC (1.69–1.76 mmol/g dry membrane), WR (63–72%) and dimen-
sional stability (DCR in the range of 13–18%). Thus their BSA
adsorption and desorption behaviors are observed. The adsorp-
tion amount of the hybrid membranes are 68.9–75.6 mg/g, close
to the BPPO(+) membrane. And the desorption percentages relate
highly with the pH values of the eluent. The BPPO-TEOS(+) mem-
brane shows excellent behaviors during both static and dynamic
adsorption and desorption procedures. The elution percentage of
BSA can reach 94.9% during the permeation mode. Therefore, BPPO-
TEOS(+) membrane is expected for applications for separation and
purification of charged biomacromolecules, drugs, or other charged
industrial wastes. Further studies concerning these applications are
under way and will be presented in our future work.
Acknowledgements
This project was supported in part by the National Science
Foundation of China (Nos. 20774090, 20974106 and 20636050),
Specialized Research Fund for the Doctoral Program of Higher
Education (No. 200803580015), and the National Basic Research
Program of China (973 program, No. 2009CB623403).
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