Desalination 327 (2013) 2431

Contents lists available at ScienceDirect

Desalination
journal homepage: www.elsevier.com/locate/desal

Effects of ordered mesoporous silica on the performances of composite

nanoltration membrane
Qiang Li , Zhaokui Li, Hui Yu, Xianhui Pan, Xuliang Wang, Yihua Wang, Jie Song
Institute of Tianjin Seawater Desalination and Multipurpose Utilization, State Oceanic Administration (SOA), Tianjin 300192, China

H I G H L I G H T S

Mesoporous silica SBA-15 was rstly utilized on the NF-membrane fabrication.

Inuences of mesoporous silica on the membrane performances were deeply analyzed.
We investigated the changes on microstructures of the SBA-15 modied NF membrane.
The inuential mechanisms on NF-membrane performances were carefully proposed.

a r t i c l e

i n f o

Article history:
Received 25 June 2013
Received in revised form 2 August 2013
Accepted 3 August 2013
Available online 27 August 2013
Keywords:
Mesoporous silica
Nanoltration membrane
Fouling resistance
Surface modication

a b s t r a c t
Surface modied composite nanoltration (MCNF) membrane was prepared by traditional interfacial polymerization approach using trimesoyl chloride and piperazine as reacting monomers, mesoporous silica SBA-15 as a
surface modication additive, for investigating the inuences of mesoporous-silica introduction on the membrane performances. Its surface properties and microstructures were carefully characterized by various analyzing
instruments. Furthermore, the rejection performance was tested using 2000 ppm of MgSO4 aqueous solution
under 1 MPa working pressure. Its fouling-resistance performance was also evaluated by using bovine serum
albumin as an organic pollutant model, based on the changes of permeate ux in the running process. The experimental results show that the introduction of SBA-15 material can obviously enable the permeate ux of the NF
membrane to be increased from 32.4 to 45.6 L/hm2, accompanied with slight decrease of MgSO4 rejection from
97.88 to 85.23%. The SBA-15 modied MCNF membrane exhibits excellent fouling-resistance performance, with
the permeate ux still retaining 72.53% of the initial ux value, after the anti-fouling test running for 270 min.
The introduction of SBA-15 signicantly improves the hydrophilicity, effective surface area and pore size of the
membrane separation layer, which is favorable for the enhancement of permeate ux and fouling-resistance
performances.
2013 Elsevier B.V. All rights reserved.

1. Introduction
In recent years, with the rapid development of industrialization and
urbanization, the scarcity of potable water has become an increasingly
serious problem [1,2]. Seawater and/or brackish water desalination as
well as wastewater treatment are generally adopted strategies for solving
this problem. Therefore, many researchers and users are focusing on the
fabrication and application of pressure-derived polymer membranes
[3,4], owing to relatively low costs, lower energy consumption, and
good controllability of the membrane separation process. Nanoltration
membrane (NF) is very attractive for its extensive applications in many
elds, including water softening, RO-process pretreatment, and the
removal of macromolecules (M.W. N 100 Da) [5,6].

Corresponding author. Tel.: +86 22 8789 9081; fax: +86 22 8789 8169.
E-mail address: qiangli_chem@hotmail.com (Q. Li).
0011-9164/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.desal.2013.08.002

At present, the main problems hindering the further development of

NF membrane application are membrane fouling and relatively low permeate ux in separation process [7,8]. Both these factors can signicantly increase the energy consumption and costs of membrane
running process. Membrane fouling usually derives from the chemical
and/or physical interactions between membrane surface and foulant
dispersed in feed water. The occurrence of fouling can also decrease
the permeate ux and membrane lifespan. Hydrophilic surface and
high zeta potential usually favor improving fouling-resistance performance [9,10], due to the reduction of mutual physical and electrostatic
interactions between the foulants and membrane surface. In addition,
permeate ux is closely related with microstructures and surface properties of NF-membrane separation layer, including effective surface
area, cross-linking degree, hydrophilicity and so on [11]. Hydrophilic
surface, low cross-linking degree and high effective surface area should
be advantageous for the improvement of permeate ux. It is because
that these factors can strengthen the water molecule-membrane

Q. Li et al. / Desalination 327 (2013) 2431

surface interactions, and improve the water transportation in NF

membrane.
Many researchers have proposed numerous strategies to synthesize
novel NF membranes for improving their permeate ux and fouling
resistance, mainly including exploring new raw materials, surface
modifying agents, and novel modication approaches [1214]. Amongst
these strategies, surface modication is the most popular and effective,
because of its controllability, exibility, and low cost. Generally, it can be
classied into two types: physical surface coating by the electrostatic
attraction, hydrogen-bond and/or van der Waals interactions [15,16];
and chemical grafting ignited by initial surface activations (such as UV,
ozone, and plasma), and/or directly chemical reactions (such as redox,
electrophilic, and nucleophilic reactions) with membrane surface functional groups [17,18]. Until now, different types of organic polymers,
monomers, nanoparticles, and zeolites have been extensively used as
modifying agents [19,20], on account of their high hydrophilicity and
favorably potential effect. For example, Seman et al. fabricated the
acrylic-acid monomer modied polyethersulfone NF membrane with
high permeate ux and excellent fouling-resistance performance by
means of UV-initiated graft polymerization technique [21]. Bai et al. prepared the TiO2-nanoparticle modied polyamide NF membrane by in
situ interfacial polymerization strategy [22]. In contrast with organic
modifying agents, their counterparts, such as metal oxide nanoparticles
and zeolites, generally have more advantages on membrane modication in terms of chemical and physical stabilities.
Since the discovery of MCM series of mesoporous silicas,
mesoporous materials with different compositions have attracted a
great deal of attentions, owing to their extensive applications in many
elds, such as catalysis, adsorption, and separation [23,24]. Amongst
them, mesoporous silica SBA-15 reported by Zhao et al. has a robust
framework, highly specic surface area (up to 1000 m2/g), controllable
pore size (4.630 nm) and ordered two-dimensional (2-D) hexagonal
mesostructures [25], compared with commonly nonporous nanoparticles. These structural properties suggest that SBA-15 has potential
applications in membrane separation process. The reason is that its high
surface area and ordered mesostructure should be favorable for improving permeate ux, and its strong hydrophilicity can enhance the antifouling performance of NF membrane. Deng and co-workers [26] introduced mesoporous carbon into aromatic-polyamide separation layer by
interfacial polymerization (IP) method. The experimental results demonstrate that the obtained composite membrane exhibits well fouling
resistance to bovine serum albumin (BSA) and high Na2SO4 rejection
(90%) performance. However, there have been no reports involving
the application of SBA-15 on membrane fabrication until now.
Herein, the inuences of mesoporous silica SBA-15 on the performances of NF membrane were rstly explored for improving the antifouling property and permeate ux. The modied polyamide composite
NF membrane (MCNF) was synthesized by IP strategy using TMC and
PIP as reacting monomers, mesoporous silica SBA-15 as a modifying
agent, sodium dodecyl sulfonate (SDS) as an additive, and polysulfone
UF membrane as the supporting layer. This research paves the way for
developing the utilization of mesoporous silica materials on water
treatment.
2. Experimental

25

received without any further purication. Polysulfone ultraltration

membrane coupons were provided by Center of Hangzhou Water Treatment. Millipore water was used in all experiments.
2.2. Synthesis of mesoporous silica SBA-15
The mesoporous silica SBA-15 was synthesized according to the reported method [25]. Typically, 4.0 g of Pluronic P123 was dissolved in
150 mL of 1.6 M hydrochloric acid solution at around 30 C. Then the
temperature of the above solution was elevated to 40 C, followed by
the addition of 10.7 g of TEOS. After being stirred at 40 C for 24 h, the
mixture was transferred into an autoclave and aged at 100 C for 24 h.
Then, the white precipitate was collected by centrifugation and dried
at 80 C. The product was obtained by removing the template at
550 C for 5 h.
2.3. Fabrications of pristine and SBA-15 modied piperazine-amide
composite NF membranes
The pristine piperazine-amide composite NF (PCNF) membrane was
fabricated by IP approach. Firstly, 5 mL of 1 g/L SDS aqueous solution
and 0.2 g of PIP were added into 100 mL of Na3PO4 aqueous solution
with pH value ca.10 under stirring. Then, the above solution was evenly
poured on a polysulfone UF membrane used as supporting layer at room
temperature. After keeping for 2 min, the residual solution was
removed from the UF membrane. After this, 100 mL of hexane solution
containing 0.2% (w/v) TMC was evenly poured on the UF membrane
wetted with PIP for the occurrence of IP reaction. Then the residual
TMC solution was removed after the reaction has lasted for 20 s. Finally,
the obtained fresh composite NF membrane was aged in oven at 75 C
for ca. 15 min for further cross linking. The obtained PCNF membrane was stored in deionized water for the following performance
evaluation.
The synthesis process of SBA-15 modied piperazine-amide composite nanoltration (MCNF) membrane was similar with that of PCNF
membrane mentioned above. Only mesoporous siliceous SBA-15 was
introduced into the fabrication process. Typically, 0.2 g of SBA-15 was
rstly dispersed in 100 mL of Na3PO4 aqueous solution with a pH
value of 10 by ultrasonic treatment. 5 mL of 1 g/L SDS aqueous solution
and 0.2 g of PIP were added into the above solution under stirring. Then,
the mixture was homogeneously poured on a polysulfone UF membrane.
After keeping for 2 min, the residual solution was removed from the UF
membrane. After this, 100 mL of hexane solution containing 0.2% (w/v)
TMC was evenly poured on the UF membrane wetted with PIP and
SBA-15 containing solution. Then the residual TMC solution was removed, after the reaction lasted for 20 s. Finally, the fabricated fresh
SBA-15 modied composite NF membrane was aged in oven at 75 C
for ca. 15 min for further cross linking, and stored in deionized water
for the following performance evaluation.
2.4. XRD measurement
For analyzing the ordering of SBA-15 mesostructure, small-angle
powder X-ray diffraction (SAXRD) pattern was recorded with a Bruker
D4 powder X-ray diffractometer (Germany) using Cu Ka radiation
(40 kV, 40 mA).

2.1. Chemicals and materials

2.5. Nitrogen sorption measurement
Tetraethyl orthosilicate (TEOS) and hexane were purchased from
Guangfu Chemical Co. Ltd. Trimesoyl chloride (TMC), triblock copolymer poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene
oxide) Pluronic P123 (M.W. = 5800), bovine serum albumin (BSA),
sodium dodecyl sulfonate (SDS), and piperazine (PIP) were all purchased from Aldrich Chemical Inc. Hydrochloric acid was purchased
from Beijing Chemical Co. Ltd. Magnesium sulfate was bought from
Kejin Fine Chemical Co. Ltd. All the above chemicals were used as

Nitrogen sorption isotherm was measured with a Micromeritics

Tristar II (USA) analyzer at 196 C for measuring the pore size and
specic surface area of SBA-15. Before measurement, the sample was
degassed at 180 C in vacuum for more than 6 h. The specic surface
area was calculated using the BrunauerEmmettTeller (BET) method.
The pore diameter (D) was determined from the adsorption branch,
according to BarrettJoynerHalenda (BJH) method.

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Q. Li et al. / Desalination 327 (2013) 2431

2.6. Transmission electron microscopy (TEM) measurement

Transmission electron microscopy (TEM) images were recorded on a
JEOL 2011 microscope (Japan) operated at 200 kV for observing the
mesostructures of SBA-15. Before TEM characterization, the samples
were dispersed in ethanol. The suspensions of the samples were
dropped on a holey carbon coated copper grid.
2.7. Infrared spectroscopy (IR) measurement
IR spectrum of mesoporous silica SBA-15 in the range of 400
4000 cm1 was collected on a VERTEX 70 FT-IR spectrometer (Bruker,
Germany) by using KBr pellet technique. The IR spectra of the fabricated
NF membranes were also measured with wavenumbers ranging
from 400 to 4000 cm1 under the attenuated total reectance
(ATR) mode for analyzing their surface functional groups. The ATR
accessory contains a ZnSe crystal at a nominal incident angle of
45, yielding a single reection on the membrane surface.
Scheme 1. Schematic of NF-membrane performance testing apparatus.

2.8. Contact angle measurement

The contact angles of the fabricated NF membranes were measured
on POWEREACH contact angle instrument (China) for evaluating their
hydrophilicity. Briey, a small droplet of puried water was delivered
onto a NF membrane, and a static image of the droplet on the membrane
surface was taken after ca. 2 s. Image analysis and contact angle computation were performed using the drop shape analysis software assuming
a circular prole of the droplet. For ensuring the accuracy of the contact
angle, the measurements were performed at 10 different locations, and
then the average value was regarded as the nal result.

in which, Cf and Cp represent feed and permeating concentrations,

respectively.

2.9. Zeta potential measurement

2.12. Evaluation of fouling resistance performance

The surface charge properties of the fabricated NF membranes were

measured with a solid surface zeta potential instrument (SurPASS,
Anton Paar). In the measurement process, the NF membranes were
rstly rinsed with puried water, and then they were determined in
0.001 mol/L of KCl aqueous solution with pH value adjusted in the
range of 311 by adding different amounts of HCl and/or KOH aqueous
solution.

For comparing the fouling-resistance performances of the PCNF and

MCNF membranes, fouling experiments were performed on the crossow type apparatus (Scheme 1). A typically experimental procedure
for resistance to BSA fouling can be described as: the NF membrane
rst run in 12 L of aqueous solution containing 20 mM/L of NaCl at
1 MPa, until its initial permeate ux (J0) became stable. Then, 2.4 g of
BSA was added into the puried water to form the synthetic foulant
(100 ppm). After running for 30 min, the permeate ux (J) was
recorded every other 30 min. Herein, NaCl was used as background
electrolyte for stabilizing the formed foulant solution. The J/J0 ratio
was used to indicate the fouling-resistance performance. For improving
the accuracy of the test results, the fouling-resistance test was repeated
for two times.

2.10. Scanning electron microscopy (SEM) measurement

The surface morphology of polysulfone UF membrane as supporting
layer was characterized using eld-emission scanning electronic
microscopy (FE-SEM) S-4800 (Hitachi, Japan) operated at 15 kV.
The fabricated NF membranes were also observed using FE-SEM
NANOSEM 430 (FEI, USA) operated at 10 kV. For avoiding the surface
charging in the measuring process, the membrane surfaces were beforehand coated with a layer of gold nanoparticles by using ion spraying
instrument.
2.11. Rejection and ux testing
The performance tests were conducted with a 2000 ppm of MgSO4
solution under 1 MPa operating pressures at ca. 20 C by using a
cross-ow type apparatus (Scheme 1). Both permeate and retentate
were recycled back to the feed tank during the tests. The permeate
water can be taken at the tip of the permeate-water pipe. Rectangular
membrane samples were placed into the test apparatus with the active
skin layer facing the feed water. The area of each membrane was around
36 cm2. The salt rejection and permeate ux of each membrane
were tested for two times, results of which have been averaged. The
permeating volumes collected for 30 min were used to describe ux
in terms of liter per square meter per hour. A standardized conductivity
meter was used to measure the salt (MgSO4) concentrations in the feed

and product water for determining membrane selectivity as given

below:
salt rejection %



Cp
 100%
1
Cf

3. Results and discussion

3.1. Structural analysis of synthesized mesoporous silica SBA-15
The structural parameters of the synthesized SBA-15 material, including mesostructure ordering, surface area, pore volume, and pore
size, were comprehensively analyzed by using XRD, nitrogen sorption,
and TEM. Three well-resolved diffraction peaks, indexed as 10, 11, and
20, can be clearly observed from the small angle XRD (SAXRD) pattern
(Fig. 1a). It suggests that the synthesized mesoporous silica SBA-15
exhibits highly ordered 2-D hexagonal mesostructure. The nitrogen
sorption results (Fig. 1b) exhibit typical type IV isotherm with type H1
hysteresis loop, suggesting that this material has typical cylindrical
pore channels. Its specic surface area and pore volume are 392 cm2/g
and 0.66 cm3/g, respectively. In addition, the nitrogen sorption isotherm (Fig. 1b) in low p/p0 range of 00.1 indicates that large amounts
of micropores were formed on the silica pore wall. Moreover, the corresponding pore size distribution curve (Fig. 1c) indicates that this material
has uniform pore size centered at ca. 9.0 nm. Combined with the SAXRD

Q. Li et al. / Desalination 327 (2013) 2431

27

Based on the above analysis, it can be demonstrated that the synthesized mesoporous silica SBA-15 has highly ordered hexagonal
mesostructure and specic surface area (392 cm2/g), uniform pore size
(9.0 nm). Generally, in the viewpoint of NF membrane fabrication, high
surface area is advantageous for the improvement of permeate ux. Uniformly cylindrical pore channel can favor the transportation of uid in
the membrane process. As a result, these structural parameters imply
that this material has potential application in water treatment.
3.2. Surface structures of fabricated PCNF and MCNF membranes

Fig. 1. Small angle XRD pattern (a), nitrogen sorption isotherm (b) and corresponding
pore size distribution (c) of the synthesized mesoporous silica SBA-15.

results, it can be concluded that its pore-wall thickness is ca. 3.5 nm.
Additionally, TEM images of the obtained SBA-15 material (Fig. 2) also
conrm that it has well ordered hexagonal mesostructure, which is
consistent with the corresponding SAXRD result (Fig. 1a). The pore size
evaluated from the TEM results is ca. 8.2 nm. It is similar with the nitrogen
sorption result (Fig. 1b and c). In addition, it was found that the particle
size of the synthesized SBA-15 is not very uniform (0.13.0 m),
conrmed by corresponding SEM results.

The surface functional groups of the fabricated NF membranes and

mesoporous silica SBA-15 were analyzed (Fig. 3) for conrming the formation of piperazineamide separation layer on the polysulfone
supporting layer and investigating the effect of SBA-15 on the
membrane-surface structure. In the case of PCNF membrane (Fig. 3a1),
the appearance of a strong peak at ca. 1620 cm1 assigned to the
stretching vibration of C=O double bond of an amide group, suggests
that the occurrence of IP reaction between PIP and TMC. The peak at ca.
1570 cm1 should be attributed to the C\N stretching vibration of the
polyamide group [27]. The peak at ca. 1720 cm1 may be related to the
polysulfone supporting layer, due to the relatively strong penetration
effect (N 300 nm) of IR light with wavenumbers around 1700 cm1
[28]. In addition, the broad peak centered at ca. 3400 cm1 is related to
the formation of \COOH groups on the membrane surface. They should
be caused by the hydrolysis of acyl chloride groups of TMC in the membrane fabrication process. These results conrm that piperazine-amide
separation layer has been formed on the support layer by interfacial
polymerization.
Additionally, ATR-IR spectrum of MCNF membrane (Fig. 3a2)
modied with mesoporous silica SBA-15 is very similar with that of
PCNF membrane. Just its intensity of the peak centered at 3400 cm1
is obviously stronger than that of pristine NF membrane (Fig. 3a1). It
is because that large amounts of SBA-15 mesoporous particles with
strong hydrophilicity were introduced in the IP process. Therefore, the
peak at 3400 cm1 for MCNF membrane (Fig. 3a2) is not only related
with \COOH groups, but also related with hydrophilic \OH groups. It
can be also conrmed by the presence of silanol (`Si\OH) group related
peaks at 3400 and 990 cm1 in the spectrum of SBA-15 (Fig. 3b). In addition, the characteristic peaks related with introduced SBA-15 cannot
be observed in the ATR-IR spectrum of MCNF membrane (Fig. 3a2). It
may be due to the lower silica content relative to a great deal of
piperazine-amide polymers formed on the membrane surface. As a result,
it can be deduced that the MCNF membrane should be more hydrophilic
than the unmodied one, owing to the abundant hydrophilic \OH
groups of introduced SBA-15.
Based on the SEM measurement results, it can be found that the
surface of polysulfone supporting layer is very at (Fig. 4a). After TMC
and PIP polymerization, the PCNF-membrane surface (Fig. 4b) becomes
slightly rough. Lots of valley-ridge structures on the membrane surface can be observed. After SBA-15 material was introduced, many
mesoporous silica particles with ca. 3.0 m were immobilized on the
surface of MCNF membrane (Fig. 4c). Except these silica particles,
some polyamide nanoparticles with ca. 4050 nm are also found on
the membrane surface. Therefore, it can be concluded that the surface
of MCNF membrane is rougher than that of PCNF membrane (Fig. 4).
Moreover, its effective surface area is correspondingly higher than that
of the pristine NF membrane, because of the modication of SBA-15
with highly specic surface area (392 cm2/g).
3.3. Surface properties of fabricated PCNF and MCNF membranes
The contact angle of piperazine-amide NF membrane (PCNF) is 48.
However, after surface modied with hydrophilic SBA-15, its contact
angle (MCNF) was obviously decreased to 35 (Fig. 5). It indicates that
the hydrophilicity of MCNF is better than that of PCNF membrane.

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Q. Li et al. / Desalination 327 (2013) 2431

Fig. 2. TEM images obtained along the [001] (a) and [110] (b) directions of SBA-15 material, respectively.

This result can be also conrmed by comparing the contact angle images
of PCNF (Fig. 5a) and MCNF (Fig. 5b) membranes.
The decrease of MCNF-membrane contact angle should be ascribed
to the following two points: Firstly, mesoporous-silica particles have
abundant \OH groups (Fig. 3b) and correspondingly strong hydrophilicity. After they were introduced in the membrane fabrication process,
many SBA-15 particles were modied on the NF-membrane surface
(Fig. 4), due to the occurrence of IP reaction. As a result, the hydrophilicity
of piperazine-amide NF membrane (MCNF) was signicantly enhanced,
and its contact angle was also correspondingly decreased. Secondly, the
modication of SBA-15 material simultaneously enhances the surface
roughness of NF membrane, which is also favorable for the contact-

angle decrease, due to the change of surface tension between membrane

surface and water droplet [28].
Furthermore, the zeta potentials of both of the two membranes were
also carefully investigated. The results (Fig. 6) show that the potential
value of PCNF membrane ranges from 2.9 to 47.5 mV with the pH
value varying from ca. 2.9 to 11. However, after the modication of
SBA-15, the zeta potential value (10.2 to 42.8 mV) of NF membrane
(MCNF) is relatively increased in the pH range of 2.811 (Fig. 6). Additionally, the isoelectric point of NF membrane (Fig. 6) is also changed
from ca. pH 3.0 to 3.3, owing to the introduction of mesoporous silica
SBA-15. Furthermore, the results suggest that the potential value of
MCNF membrane is obviously higher than that of PCNF membrane in
the general pH range (68) of seawater and/or brackish water (Fig. 6).
Generally, the membrane surface with zeta potential more near to neutral can decrease the electrostatic interactions with charged foulants,
due to the decrease of the amounts of its surface charges. On the other
hand, the SBA-15 modication caused higher potential should exhibit
strong anti-fouling property to hydrophobic organic foulants, owing to
the weak interactions between hydrophilic \OH groups and organic
foulants. Therefore, it can be concluded that MCNF membrane may
have stronger anti-fouling property than that of PCNF membrane [29].
The relatively lower zeta potential of PCNF membrane mainly
derives from the presence of many \COOH groups on the surface conrmed by the corresponding ATR-IR results (Fig. 3a). These \COOH
groups can dissociate into negatively carboxylate ions in aqueous solution, which makes the membrane surface exhibits relatively high
negative-charge density. Only in higher acidity of aqueous solution,
the dissociation process of \COOH groups can be resisted and the
membrane-surface charge turns into neutral. Therefore, the isoelectric
point of PCNF membrane is located at ca. 3.0 of pH (Fig. 6). The modication of mesoporous silica enables the membrane surface to have
abundant neutral \OH groups, and these groups decrease the negative
charge density of membrane surface in aqueous solution in some extent.
As a result, the zeta potential of MCNF membrane was obviously
enhanced. Correspondingly, its isoelectric point was also shifted to 3.3
of pH, due to the decrease of the amounts of carboxylate ions.

3.4. Effects of mesoporous silica SBA-15 on separation performance

Fig. 3. Normalized ATR-IR spectra of the fabricated NF membranes (a) and synthesized
mesoporous silica SBA-15 (b). (a1) PCNF membrane; (a2) MCNF membrane.

The separation-performance testing suggests that the rejection of

PCNF membrane to 2000 ppm of MgSO4 aqueous solution is ca.
97.88% at 20 C and 1 MPa working pressure. Its corresponding permeate ux is ca. 32.4 L/hm2. However, after modifying mesoporous silica
on the pristine NF membrane, the permeate ux (MCNF membrane) is
obviously enhanced to 45.6 L/hm2 under the same testing conditions
as above. Simultaneously, its salt rejection is decreased from 97.88 to
85.23%.

Q. Li et al. / Desalination 327 (2013) 2431

29

These results indicate that the pristine piperazine-amide NF (PCNF)

membrane has relatively high salt rejection and low permeate ux, because of the high compactness and relatively low effective surface area
of piperazine-amide separation layer. The introduction of mesoporous
silica SBA-15 makes the pore size of separation layer partly enlarged.
Moreover, the high specic surface area of SBA-15 (392 cm2/g) and
large membrane-surface roughness endow the obtained MCNF with
high effective surface area. These structural changes make its salt rejection decrease to ca. 85.23% and permeate ux increase to 45.6 L/hm2.
In addition, the increasing hydrophilicity of MCNF membrane conrmed by contact-angle results is also favorable for the improvement
of permeate ux, due to the strongly hydrogen-bond interactions
between the water molecules and \OH groups.
3.5. Effects of mesoporous silica SBA-15 on the fouling-resistance
performance
The fouling-resistance testing results (Fig. 7) suggest that the permeate ux of PCNF membrane obviously decreases with the elongation
of running time in 100 ppm of BSA aqueous solution under 1.0 MPa
working pressure and 20 C. Especially in the initial period (30 min)
of the anti-fouling experiment, its permeate ux drastically decreases
to 75.86% (J/J0) of the initial value, suggesting that many BSA molecules
adsorbed on the PCNF membrane surface. Then, the decay rate of permeate ux becomes relatively slow, and its J/J0 ratio is nally decreased
to 63.81% after running for 270 min. However, in the case of MCNF
membrane modied with mesoporous silica SBA-15, its permeate ux
decreased to 80.80% of the initial value after lasting for 30 min
(Fig. 7). It is higher than that (75.86%) of the PCNF membrane. With
the further elongation of running time, the permeate-ux decreasing
rate becomes very slow comparing with PCNF membrane. Its J/J0 ratio
is nally decreased to 72.53% (Fig. 7) after running for 270 min, which
is also higher than that of the unmodied one. These results suggest
that the introduction of SBA-15 can obviously improve the fouling resistance performance of piperazine-amide NF membrane.
Generally, the NF membrane fouling mainly derives from the
stacking and van der Waals interactions between hydrophobic functional groups of BSA and piperazine-amide polymer, such as phenyl
and alkyl groups. In addition, another important factor is the electrostatic attractions between BSA molecules and membrane surface. The improvement on the fouling resistance performance of MCNF membrane
modied with SBA-15 should be mainly attributed to the changes of
surface properties, including the improvement of surface hydrophilicity
and enhancement of zeta potential. Its excellent surface hydrophilicity
conrmed by the contact angle results can weaken the interactions between BSA and NF membrane surface. It is because that the introduction
of mesoporous silica SBA-15 increases the amounts of hydrophilic \OH
groups and decreases the amounts of hydrophobic groups on the membrane surface. On the other hand, the introduced SBA-15 material
enhances the zeta-potential value of MCNF membrane (Fig. 6) and decreases the amounts of negative charges from the dissociation of
membrane-surface functional groups, which maybe weaken the electrostatic attractions between BSA foulants and membrane surface.
3.6. Formation process of SBA-15 modied MCNF membrane

Fig. 4. FE-SEM images of the UF supporting layer (a), fabricated PCNF (b) and mesoporous
silica modied MCNF membranes (c).

In the fabrication process of MCNF membrane, PIP molecules and

SBA-15 particles are rst uniformly dispersed on the supporting layer
(polysulfone UF membrane). Simultaneously, many PIP molecules are
also adsorbed on the surfaces of SBA-15 particles via the hydrogenbond interactions between \NH\ groups of the former and \OH
groups of the latter. After TMC containing hexane solution was introduced onto the supporting layer wetted by PIP and SBA-15, the
piperazine-amide separation layer is formed by IP reaction between
TMC and PIP molecules. In the same time, the polymerization reaction
also occurs around the SBA-15 particles adsorbed with PIP molecules.

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Q. Li et al. / Desalination 327 (2013) 2431

Fig. 5. Contact-angle images of the fabricated PCNF (a) and mesoporous silica modied MCNF membranes (b).

As a result, the SBA-15 particles were immobilized by the formed

piperazine-amide polymers and uniformly embedded in the separation layer. This structure is advantageous for improving the stability
of SBA-15 and preventing its loss in the membrane running process.
Subsequently, the aging process at 75 C can further prompt the
polymerization of TMC and PIP, and enhance the cross-linking degree
of piperazine-amide separation layer. It is favorable for the improvement of salt rejection. Finally, the mesoporous silica modied NF membrane is successfully fabricated by the above process.

4. Conclusions
The introduction of ordered mesoporous silica SBA-15 can obviously
improve the permeate ux of piperazine-amide NF membrane, accompanied with the decrease of salt rejection. It is because that the larger
pore sizes (ca. 9 nm) and excellent hydrophilicity of the introduced
SBA-15 can improve the transportation of water molecules in separation layer and strengthen the interactions between water molecules
and membrane surface, respectively. Moreover, the introduction of
SBA-15 with high specic surface area (392 cm2/g) increases the
effective membrane surface area, which is also favorable for the
enhancement of permeate ux. On the other hand, the addition of
SBA-15 partly enlarges the pore size of NF membrane, which leads to
the decrease of salt rejection.
Additionally, mesoporous silica SBA-15 can also signicantly improve the NF-membrane fouling resistance to BSA. It is because that
SBA-15 improves the membrane hydrophilicity, which can weaken
the chemical and/or physical interactions between BSA molecules and
piperazine-amide polymers. Furthermore, the introduction of SBA-15
increases the zeta-potential value and decreases the amounts of negative charges of NF membrane surface, which can also decrease the electrostatic attractions between BSA molecules and membrane surface.

Acknowledgments

Fig. 6. Zeta potential curves of the fabricated membranes under different pH values.

The authors thank the nancial support of the Young Oceanic Science
Foundation of State Oceanic Administration (SOA) (No. 2012448), and
the Basic Scientic Research Funds for the State-level Scientic Research
Institute (Nos. 2013-G4, 2012G01).

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Fig. 7. Fouling-resistance performances of the fabricated PCNF and MCNF membranes to

100 ppm of BSA solution at 1.0 MPa working pressure.

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