Desalination 298 (2012) 3441

Contents lists available at SciVerse ScienceDirect

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

Preparation and characterization of a novel PA-SiO2 nanoltration membrane for raw

water treatment
Limei Jin a, b, Wenxin Shi a, Shuili Yu a, c,, Xuesong Yi a, Nan Sun a, Cong Ma a, Yinsong Liu a
a
State Key Laboratory of Urban Water, Resource and Environment, School of Municipal and Environmental Engineering, Harbin Institute of Technology, Harbin 150090, China
b
School of Food Science, Heilongjiang Bayi Agricultural university, Daqing,163319, China
c
State Key Laboratory of Pollution Control and Resources Reuse, Tongji University, Shanghai, 200092, China

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

Article history: A novel nanoltration membrane containing SiO2 nanoparticles was prepared with poly(amidoamine)
Received 9 February 2012 (PAMAM) dendrimer and trimesoyl chloride (TMC) by interfacial polymerization on polysulfone (PSF) ultra-
Received in revised form 24 April 2012 ltration membrane. The FTIR-ATR, FESEM, XPS, TGA and contact angle analyzer were employed to character-
Accepted 30 April 2012
ize the surface morphology, physical and chemical properties of PA-SiO2 membrane. The prepared conditions
Available online 28 May 2012
should be controlled as PAMAM concentration 0.2% (wt.), TMC 0.2% (wt.) and the interfacial polymerization
Keywords:
time nearly 90s. The addition of nano-SiO2 in the skin layer improved thermal stability, hydrophilicity and
Nanoltration membrane enhanced the membrane permeation properties without loss of rejection rate. The order of salts rejection
Interfacial polymerization rate is Na2SO4 > MgSO4 > MgCl2 > NaCl, which indicated that the PA-SiO2 was nagatively charged. The zeta
PAMAM potentials for PA-SiO2 membranes were more negative than that of PA membrane for nano-SiO2 surface
SiO2 with more negatively charged hydroxyl groups. The nano-composite NF membrane is particularly suitable
Raw water for treating acidic feeds and separating salt solution containing bivalent anions. The anti-fouling abilities
were enhanced for PA-SiO2 membrane when treating with raw surface water.
2012 Elsevier B.V. All rights reserved.

1. Introduction nanoltration membrane was made of polymer. The organic polymer

Drinking water scarcity is expected to grow worse globally espe-
cially in the coming decades. New methods with lower cost, less
energy and minimizing the use of chemicals and impact on the envi-
ronment will be popular to purify water [1]. Nanoltration (NF) is a
type of separation process between reverse osmosis and ultraltra-
tion (UF), which is a promising technology since it requires less ener-
gy than traditional reverse osmosis membranes and a proper pore
size to separate small molecular substances compared with UF pro-
cess. It has introduced a new perspective for the treatment of indus-
trial efuents contaminated with organics or salts, and has been
widely applied in water treatment, such as in chemical and pharma-
ceutical industries, biotechnology, environmental protection and
water treatment and so on[2]. In applications of drinking water in-
dustry, NF has been widely used for removal of hardness, natural
organic material (NOM)[3], micropollutants such as pesticides[4],
DDT [5] and VOCs, viruses and bacteria, nitrates and arsenic[6,7],
uranium[8], dissolved organic nitrogen (DON)[9] etc. [10]. For nano-
ltration membrane prepared with interfacial polymerization pro-
cess, the skin layer is the key factor for determining the total
properties of composite nanoltration (NF). Most of commercial
Corresponding author at: School of Municipal and Environmental Engineering,
Harbin Institute of Technology, Harbin, 150090, China. Tel.: + 86 0451 86282101.
E-mail address: Yushuili.cn@gmail.com (S. Yu).
has many advantages, such as extensive sources, convenient manu-
facture, low cost, and easy to achieve the industrialization, while it
also has the disadvantage to overcome, such as bad thermostability,
anti-fouling and poor anti-swelling etc. In recent years, many new
types of organic/inorganic hybrid materials were explored to
combine the desired properties of inorganic and organic, improving
the thermal and mechanical properties, dimensional stability,
electrochemical and anti-swelling performance, hydrophilicity of in-
organic ones, and the exibility and ductility of organic polymers
[1114]. For inorganic nanoparticles, which have a higher specic
area and lots of negatively charged hydroxyl groups existing on the
surface, it can bring new good properties for the composite materials.
Several types of inorganic materials have been used as additives in
organic polymers in UF and NF membrane preparation process, which
includes titanium dioxide (TiO2)[1517], zirconium dioxide (ZrO2)
[18], Al2O3[19], and Al2O3 and TiO2 mixture[17], and were also used
in nanoltration preparation etc. Nanoscale titanium dioxide (TiO2)
nanoparticles have received much attention and been used in water
treatment membrane preparation primary for its photo-catalyst
properties, which has properties to decompose organic compounds
and possibly overcome the fouling phenomena in the membranes.
Silicon dioxide (SiO2) [2,15,1820] has also been widely used in ltra-
tion membrane preparation, such as PEGSiO2[21], PESSiO2[22],
PVA/SiO2 membrane[12]. The silicon dioxide nanoparticles have
been treated rst to get hydrophilic or hydrophobic groups, which

0011-9164/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2012.04.024
 L. Jin et al. / Desalination 298 (2012) 3441
Fig. 1. Chemical structure of PAMAM dendrimer ((a) Generation 0, (b) Generation 1).
is convenient to modify the properties of the polymer. SiO2 nano-
particles have a wide resource and lower price than Al2O3 and TiO2
nanoparticles, which was adopted here to prepare nanoltration as
ceramic llers.
Interfacial polymerization monomers selection is also very impor-
tant for the selective layer synthetized from them and the skin layer
determining the total properties of nanoltration membrane [2,21].
Polyamide-amine (PAMAM) dendrimer has a global hyperbranched
structure and multi-active NH2 group sites. The quantities of
NH2 groups of PAMAM molecules increase exponentially with gen-
erations. Now few researchers prepared NF membranes with dendri-
mers. Li Lianchao et al. [20] prepared NF membrane with PAMAM
dendrimer and the resulted membrane displayed good performance.
PAMAM also has unique inner cavity properties suitable to be used
as a carrier, which has been widely used in the eld of medical,
such as drug delivery, sustained-release and controlled-release
agents [18,20]. Thus the inner cavity should also be expected as a car-
rier for SiO2 nanoparticles to modify the NF membrane's characters.
In this work, we attempted to prepare composite NF membrane
with nano-SiO2 by interfacial polymerization. PAMAM was adopted
as aqueous monomer; trimesoyl chloride (TMC) dissolved in hexane
solvent was used as organic monomer and PSF (polysulfone) UF
membrane as substrate. The interfacial polymerization process was
studied and composite membrane with desired separation properties
was obtained and characterized. Finally, the resulting PA-SiO2 was
applied to treat with raw water from Songhua River to evaluate its
separation performance.
2. Experiments
2.1. Materials
PAMAM (G0) was used as aqueous monomer and provided from
Sigma-Aldrich Co. Ltd. (USA) with ethylenediamine as core. The
chemical structures PAMAM dendrimer are shown in Fig. 1[23]. The
substrate membrane used in this study was polysulfone (PSF) UF
with MWCO 30,000 Da membrane supplied by Development Center
of Water Treatment Technology, State Oceanic Administration
(Hangzhou, China). Trimesoyl chloride (TMC) was afforded from the
Odyssey Chemical Engineering Limited Company (Beijing, China). A
commercial form of nano-SiO2 (BET area 200 m 2/g, diameter of parti-
cles 15 nm, containing hydrophilic groups) was provided from
Dixiang Chemical Engineering Limited Company(Shanghai, China).
N-hexane was purchased from Guoyao Groups (Beijing, China). All
other reagents and chemicals were analytical grade and used without
further purication. Deionized water was used for membrane prepa-
ration and permeation experiments.
35
2.2. Raw water
Raw water used in this study was obtained from Songhua River,
Harbin, Heilongjiang province, China. The source water was pre-
ltered using a 0.45 m MF membrane before NF ltration tests to
avoid clogging and enhance the useful life time. The ltrated water
quality after microltration and water output quality treated by NF
membrane in this study were shown in Table 2. Water quality analyt-
ical methods adopted here are on the basis of GB/T5750.3-2006, China.
2.3. Preparation of PA-SiO2 nanocomposite NF membranes
The PA nanocomposite membranes were prepared with interfacial
polymerization method. In order to overcome the SiO2 aggregation
and increase its dispersibility in the casting solution, SiO2 solution
preparation method was modied according to document [24]. An ap-
propriate amount of SiO2 was added to a 100 mL 2.0% sodium dodecyl
sulfate (SDS) solution, in which PAMAM (G0) content was between
0.05% (wt.) and 0.25% (wt.). After 1 h of vigorous stirring and ultrason-
ic vibrated at 40 kHz, a uniform and homogeneous solution was
obtained. The PSF support membrane was immersed in the aqueous
solution above for about 10 min then was taken out; the wet mem-
brane was rolled with a rubber roller to get rid of the excess amounts
of aqueous solution remaining on its surface. Next, the membrane was
immersed into the n-hexane solution of TMC for 90 s to produce inter-
facial polymerization, resulting in the formation of a thin lm of PA on
the top layer of PSF support. The composite membranes were subse-
quently cured in an air-circulation oven at a given curing temperature
for a certain time to approach the desired stability of the formed
structure. The membranes were thoroughly washed and kept with de-
ionized water before carrying out evaluation studies.
2.4. Membrane characterization
The presence of functional groups on the membrane surfaces was
analyzed by FTIR-ATR technique (Spectrum one B, Perkin Elmer Inc,
Table 1
Contact angle of PA-SiO2 membrane.
SiO2 content/% (wt.) Contact angle (deg) Flux(L (m2 h) 1) Rejection (%)
0 77.68 7.8 92.3
1 66.84 13.99 77.57
1.5 65.46 15 78.5
2 64.31 5.38 89.95
2.5 66.45 7.11 72.74
3 70.16 12.96 55.24
36 L. Jin et al. / Desalination 298 (2012) 3441

Table 2 the stirred cell, solution reservoir was lled with determinant solution
Output water quality of microltration and nanoltration by PA-SiO2 membrane. or water. Then the blender was turned on and the membrane was
Water quality Treated water Treated water Water measured under the expected condition for about 10 min. Repeat the
by MF by NF standard course above to test other membrane properties. The results were cal-
Colority 12 6 15 culated as follows according to the record ltration time and perme-
Turbidity (NTU) 0.346 0.2 1 ation volume.
pH 7 7 6.58.5 The ux (J) may be described by the following equation:
COD (mg/L) 2.2 0.7 50
NH3-N (mg/L) 1 0.9
J V=At 1
Conductivity(s/cm) 302 125.4

where J is the permeate ux, V the volume of permeation water, A

USA). The surface and cross-section of the resulted membranes were
measured by FESEM on QUANTA 200 FEG MK2 (FEI Company, Hol-
land). The XPS analysis was done on PHI 5700 ESCA System (Physical
Electron Company, USA), which employs AlKa X-ray source
(hv = 1486.6 eV). Wide scan was recorded with a pass energy of
187.85 eV, and narrow scan with a pass energy of 29.35 eV. Relative
atomic concentrations of the nanocomposite membrane surface
were calculated by normalizing peak areas with the elemental sensi-
tivity factor data provided from the database of the instrument. Sur-
face hydrophobicity/hydrophilicity of the unmodied and modied
membranes were determined by contact angle value of a water
drop deposited on the membrane surface using contact angle analyz-
er (SL200B, Shanghai, China). Thermal gravimetric analysis (TGA)
was carried out using ST449 TG/DSC (NETZSCH Company, Germany)
to determine the thermal stability of membrane. Measurements
were made by heating from 30 to 1000 C under a N2 atmosphere at
a heating rate of 10 C min 1 with about 10 mg sample. Zeta poten-
tial reects the electrical property of the membrane. The sample
was cut as 55 mm 25 mm strip, then it was placed on the testing
table and the zeta potential was measured by solid electric sports
analyzer (Surpass, Anton Par GmbH, Austria).
2.5. Permeation experiments
The permeation ux and rejection of the nanocomposite mem-
branes were determined on the batch type ltration apparatus
(XFUF07601, Millipore Co., USA). The schematic diagram of the
dead-end ltration system was shown in Fig. 2. Circular membrane
samples have a diameter of 76 mm and the effective membrane area
was around 40 cm 2. The membranes were placed in the stirred cell
with the skin active layer facing the feed. Then each membrane was
initially compacted for 20 min under 0.60 MPa (pure water ux stabil-
ity requires only about 20 min). Fixing the compacted membrane in
the membrane area and t is the permeation time. Rejection was cal-
culated with the following equations:
R C f C P =C f  100% 2
where Cp is the permeate concentration and Cf is the concentra-
tions of the feed solution. In our experiment, all membrane samples
were prepared and tested with a total of three duplicated membranes
at least for NF performance, and the results presented were the aver-
ages of these measurements. When treated with raw water, the per-
meation water should be recycled to the stirred cell by a pump to
keep the concentration of feed nearly unchanged.
3. Results and discussion
3.1. Characterization of PA and PA-SiO2 membrane
The FTIR-ATR spectra of PSF substrate UF membrane, PA and
PA-SiO2 nanoltration membrane were shown in Fig. 3. PA-SiO2
nanocomposite membrane was prepared with 2.0%(wt.) SiO2
nanoparticles in aqueous solution. As we know that interfacial
polymerization reaction between PAMAM and TMC monomers can
produce PA active layer. Compared with PSF, the FTIR spectra clearly
present the primary amide (C O) at 1658 cm 1, stretching NH
amide at band 3300 cm 1 and the amide II (CN stretch) at
1585 cm 1. The peaks above conrmed the polymerization reaction
and occurred between PAMAM and TMC. From PA-SiO2 curve, since
the characteristic peaks SiOSiwere stretching bands at the
region of ~ 1100 cm 1[22], the peak at 1076 cm 1 was strengthened
greatly which probably represents for SiOSi bands existing
on the membrane surface overlapping with other peaks.
The surface morphologies of PA and PA-SiO2 nanocomposite
membranes were displayed by FESEM micrographs in Fig. 4. After

Feed

Conductivity meter
Stirred cell

Magnetic stirrer Data processing system

Electronic balance

Nitrogen tank

Fig. 2. The schematic diagram of the dead-end ltration system.

 L. Jin et al. / Desalination 298 (2012) 3441 37

aqueous solution, the nanoparticles were uniformly distributed on

PSF the membrane surface under 5000 and 40,000 magnication, the
membrane surface was rough and full of holes which can be seen
distinctly. To further observe the surface morphology of SiO2
PA nanoparticles dispersed in the skin layer, the membranes were ob-
served under 100,000 magnication. The nanoparticles were well
distributed in the top layer.
PA-SiO2 The quantitative information of nano-SiO2 nanoparticles and other
elements in the nanocomposite membrane was measured by XPS
3300
method and the results were shown in Fig. 5. The XPS spectra for car-
1658 1386
1585 bon (289.12 eV), nitrogen (403.9 eV), oxygen (536.5 eV) and silicon
(108.63 eV for 2p) were presented in Fig. 5. The other peak of silicon
(153.39 eV for 2 s) would not be shown here. The oxygen was
1076
corresponded to CO in the skin layer or SO in the ultralltration
substrate; the peak at 533.5 eV was assigned to the SiO groups.
The peak around 108.63ev binding energy was found from SiO2 mod-
Wave number (cm-1) ied membrane, which is from SiOSi bond. The testing PA-SiO2
membrane was prepared with 1.0% (wt.) mass concentration of SiO2
Fig. 3. FTIR spectra for PSF, PA and PA-SiO2 membrane.
in the aqueous solution. The content of the elements in the com-
posite membrane was as follows: C: 63.57%, O: 27.03%, N: 5.98%,
interfacial polymerization between aqueous and organic monomers Si: 2.95%, S: 0.47%. The sulfur elements might come from the
onto PSF substrate, the top layer of pure PA nanoltration membrane base ultraltration membrane for sulfur elements existing in the
is dense, rough, and nely dispersed nodular structures, packed tight- sulfone group.
ly by the spherical globules under 100,000magnication, and the Fig. 6 showed TGA curves of pure PA and PA-SiO2 membrane. The
hole cannot be seen clearly. From the graph of PA-SiO2 nano- SiO2 additive amount is about 1% in the aqueous solution. The TGA
composite membrane prepared with 1.0%(wt.) SiO2 nanoparticles in curve of PA and PA-SiO2 membranes were similar with two major

a) PA (100,000) b) PA-SiO2 (5,000)

c) PA-SiO2 (40,000) d) PA-SiO2 (100,000)

Fig. 4. FESEM micrograph of membranes.

38 L. Jin et al. / Desalination 298 (2012) 3441

a) Carbon b) Nitrogen

Intensity

Intensity
Binding energy (eV) Binding energy (eV)

c) Oxygen d) Silicon
Intensity

Intensity

Binding energy (eV) Binding energy (eV)

Fig. 5. XPS spectra for carbon, nitrogen, oxygen and silicon for PA-SiO2 nanocomposite membrane.

weight loss regions. For PA and PA-SiO2 membrane, the rst region
was at a temperature of 380483 C and the second weight loss re-
gion was at a temperature around 510562 C. For the rst transition
region nearly 400 C, the total weight loss at this stage was about 68%,
62% for PA and PA-SiO2 respectively due to the degradation of poly-
amide(PA) existing on the top of substrate. The peak of the second
stage at around 510 C562 C was due to the cleavage backbone of
PA polymer lm. The total weight loss was about 75% for pure PA
membrane and 73% for PA-SiO2 (1.0%) membranes at about 600 C.
(2) PA-1.0%SiO2
(1) PA
Weight /% (wt.)
In a word, the degradation peaks of PA-SiO2 composite nanoltration
membrane shifted toward higher temperatures which indicatesthat
the PA-SiO2 membrane has a higher decompose temperature. The
thermal stability would be improved due to the additive effect of
SiO2 llers in the PA membranes.
To characterize the charge performance of the membrane, salt rejec-
tion experiment with PA and PA-SiO2 membrane was investigated for
the surface charge can be judged by the order of the salt rejection.
Four kinds of salt solutions were used in the experiment. They
are MgSO4, MgCl2, NaCl, Na2SO4, whose mass concentration is all
1000 mg/L and ltrate pressure 0.5 MPa. The membrane adopted here
was prepared from generation 0. The salts rejections order of these
membrane was Na2SO4 > MgSO4 > MgCl2 > NaCl. For treating with
CaCl2 solution (500 mg/L), the ZETA potentials of PA-SiO2 and pure PA
membranes was 14.33mv and 2.92mv when the testing salt
PH = 7.10. The zeta potentials for PA-SiO2 membranes were more neg-
ative than that of PA membrane in the same salt solution for nano-SiO2
surface with more negatively charged hydroxyl groups. The rejection

for bivalent anions SO42 is higher than other electronegative ions.

These results demonstrated that PA-SiO2 is negatively charged. Multiva-
(2) lent cation Mg 2+ has an opposite charge to membrane and a strong
binding force to membrane, which resulted in rejection rate of MgSO4-
and is less than that of Na2SO4.
(1)

3.2. Effect of preparation parameters upon rejection and ux

Temp /oC Fig. 7 showed ux inuenced by PAMAM aqueous solution con-

centration. The ux decreased and salt rejection rate increased with
Fig. 6. TGA curves of pure PA and PA-SiO2 membrane. PAMAM concentration. The rejection rate of the membrane reached
 L. Jin et al. / Desalination 298 (2012) 3441
Rejection
Flux
Flux /( L (m2 h)-1)
Rejection/%
Concentration of PAMAM/%
Fig. 7. Effect of variation in PAMAM concentration on ux and salt rejection.
maximum (90.2% for Na2SO4) for 0.20% PAMAM concentration, while
the ux was minimum (6.0 L/m 2 h). At lower concentration stage of
PAMAM (0.2%), the extent of ux decline and rejection increase
with PAMAM concentration was signicant than that at higher
PAMAM concentration (0.2%). This observation can be explained
following the work of Freger [25] on PA lm formation kinetics and
Nadler and Srebnik [21,26]. With increase in PAMAM concentration,
the formation of thin barrier layer tends to be the maximum thick-
ness and density since the lm thickness remains almost unchanged,
which results in increasing in rejection and lowering in ux. Thus,
PAMAM concentration 0.2% was adopted here. The interfacial poly-
merization speed was inuenced by the aqueous and organic mono-
mers diffusion speed; it is expected that the inuence of variation in
TMC concentration on ux and salt rejection has similar trend with
that of PAMAM. This hypothesis was conrmed in the experiments.
The TMC should be controlled about 0.2% and the relative experimen-
tal data were not listed here.
In order to investigate the effect of interfacial polymerization time
of the TMC and PAMAM solution, several nanoltration membranes
were prepared with different contact time from 30 s to 150 s. The
values of water permeability ux and salt rejection were presented
in Fig. 8. It can be seen that water permeability decreased with in-
creasing contact time, while the values of Na2SO4 rejection rate
were in opposite trend. Song [27] reported that the membrane per-
meability decreases rapidly while the retention rate increases rapidly
during the initial period of time of interfacial polymerization, then
Rejection
Flux
Flux /( L (m2 h)-1)
Rejection/%
Contact time/s
Fig. 8. Effect of interfacial polymerization time on ux and salt rejection.
39
they all nearly kept unchanged. It indicated that the formation of a
dense cross-linking barrier will block the diffusion of PAMAM to
react with TMC. It can be concluded that interfacial polymerization
process was a self-limiting phenomenon existing in the diffusion-
controlled interfacial polymerization [28]. To get a higher rejection
membrane, the proper contact time should be controlled near 90 s.
3.3. The effect of SiO2 content on contact angle
The contact angle represents the hydrophilicity/hydrophobicity of
the membranes of composite nanoltration. The testing solution was
Na2SO4 (1000 mg/L) and ltration pressure 0.5 MPa. The contact an-
gles values were measured and the results were shown in Table 1.
As we can see the contact angle rstly decreased with additional
amount of nano-SiO2 in the aqueous solution and the ux of the
membrane would improve nearly 100% percent. This is because a
lot of silanol or hydroxyl groups covered on the surface of the SiO2,
which contributes to improve the hydrophilicity of the membrane.
However, after SiO2 content exceeded above 1.5%, the contact angle
increased on the contrary. With the content of SiO2 increasing, the
particles quantities adsorbed and inlayed on the surface of membrane
increased greatly which results in the contact angle lower and hydro-
philicity strengthened. However, with the content of SiO2 nano-
particles in aqueous solution exceeding to a certain value, the
viscosity of silica sol further increased and reunion happened. The
specic area of the aggregate decline will result in decreasing the
hydroxide radical quantities and augment the contact angle. From
the values of Table 1, the percent of SiO2 nanoparticles should be con-
trolled at nearly 1.01.5% (wt.) in PA-SiO2 membrane.
3.4. Effect of operating conditions on NF membrane performance
Figs. 9 and 10 demonstrated the inuence of operating conditions
on membrane performance, i.e. operating pressure on pure water ux
and concentration of feed Na2SO4 (1000 mg L 1) on rejection rate.
The pure water ux of NF membrane with and without SiO2 was
shown in Fig. 9. It showed that the ux was a linear function with
the operating pressure in testing pressure range. The volume ux
through these pores may be described by the HagenPoiseuille equa-
tion for viscous ow.
The ux of PA-SiO2 membranes was a little higher than that of
pure PA membrane. The reason should be that the contact angle de-
creased and hydrophilicity increased when the SiO2 nanoparticles
blended in the skin layer. The hydroxy existing on the surface of the
SiO2 nanoparticles contributed to decrease the contact angle and the
roughness improving increase in the hydrophilicity of the membrane.
PA
PA- SiO2
Flux /( L (m2 h)-1)
Operating pressure /MPa
Fig. 9. Pure water ux of PA and PA-SiO2 membranes.
40 L. Jin et al. / Desalination 298 (2012) 3441

K+
Ca2+
PA-SiO2
Mg2+
PA
Rejection rate/%

Rejection/%
PH
Concentration of Feed solution (g/L)
Fig. 12. Effect of PH on rejection rate of different ions.
Fig. 10. Na2SO4 rejection of PA and PA-SiO2membrane as a function of feed Na2SO4
concentration.
on the membrane surface interacting with ions in the feed. As the pH
in feed decreased, amino groups on membrane surface combined
Fig. 10 showed that the reason for the decrease of the rejection
with H + and changed into RH3N + and R3HN +[20] and the membrane
ratio with salts concentration is that effective area of the membrane
displayed positive charge. The electrostatic repulsion between
pore becomes larger due to reduction of the thickness of the electrical
charged membrane and bivalent anion SO42 in the feed decreased
double layer. At the same time, with the increasing of concentration,
resulting in enlarged pore size which resulted in a higher ux for
the -potential increases slowly and the negative surface charge in-
K +. Meanwhile, the electrostatic repulsion between Ca 2+, Mg 2+
creases for excess adsorption of cations onto the NF membrane sur-
and charged membrane increases for like charges repelling which de-
face, and the repulsive electrostatic forces also decrease between
creased the ux of Ca 2+and Mg 2+. In contrast, increasing the pH in
the membrane surface and the bulk of salt solution; at the same
the feed, NH3+ cannot be able to transfer from NH2 groups and the
time, the ions in the solution repulse each other, and therefore the
membrane appears nagatively charged which increases and the elec-
salt rejection rate decreased with the increasing of salt concentration.
trostatic repulsion between membrane and negative ions, resulting in
The nanoparticles were embedded in the organic polymer structure,
the shrinkage of pores on the membrane surface and a lower ux.
which leads to the skin layer of PA-SiO2; nanoltration was less
Fig. 12 showed the effect of pH of the feed on rejection rate for the
dense than pure PA membrane. Thus the rejection of PA-SiO2
PA-SiO2 membrane (other conditions are similar with listed above). It
nanoltration was a little lower than the pure PA membrane.
can be seen that increasing the pH in the feed, the rejection rate of all
of these three ions (Ca2+, Mg2+, K+) decreased. This is because the neg-
3.5. Effect of PH on NF membrane performance ative charge on the membrane surface increase would increase the re-
pelling force between the solutes and membrane surface and the pore
Fig. 11 showed the effect of pH in the feed on solution ux for the size shrinks. Therefore the resulting PA-SiO2 was particularly suitable
PA-SiO2 membrane (pH in the solution was adjusted from 2 to 9 using for treating acidic feeds and salt solution containing bivalent anion.
sodium hydroxide and hydrochloric acid. The pressure applied was
xed at 0.50 MPa. The feed solution is 1000 mg L 1 K2SO4, CaCl2, 3.6. Application on surface water with PA-SiO2 membrane
MgCl2 solution, respectively). Ca 2+and Mg 2+ ions exhibit higher
uxes, when the pH is neutral (pH = 7.37), compared with the ux The results of raw water ltration test by pure PA membrane and
at pH 3.68 or 10.0 using the same membranes, especially, and the PA-SiO2 membrane (SiO2 additive amount is 1% (wt.)) were shown in
ux (at pH 3.68) is lower than the ux at pH 7.37. This implies the Fig. 13. Both ux of the PA and PA-SiO2 displayed decline trend and
change of amino groups (NH2) groups and/or tertiary amino groups
PA
K+ PA-SiO2
Ca2+
Mg2+
Flux /( L (m2 h)-1)
Flux /( L (m2 h)-1)

Time/h
PH
Fig. 13. Flux decline behaviors of PA and PA-SiO2 membrane according to the ltration
Fig. 11. Effect of PH on ux of different ions. time.
 L. Jin et al. / Desalination 298 (2012) 3441
the former one showed a greater amount of ux decline compared
to hydrophilic PA-SiO2 membrane. Surface water contains three
potential membrane fouling categories, including microbial content
(bacterial, viruses etc.), organics and inorganics (humic acid, min-
erals). The addition of SiO2 nanoparticles to the membrane signi-
cantly increased the anti-fouling property of the PA membrane. This
is because a lot of hydroxyl groups lied on the surface of SiO2
nanoparticles which would increase the negative charges on the
surface of the membrane which weaken the force between the
negatively charged micelles and the surface of the membrane. The
hardness remove rate is about 58.75% with the PA-SiO2 membrane.
4. Conclusion
PA-SiO2 composite membranes were prepared by interfacial poly-
merization method with PAMAM and TMC as aqueous and organic
monomers, respectively. The inuence of nano-SiO2 on composite
membrane was investigated. The main conclusions were listed as
follows:
1. The PA-SiO2 nanocomposite membranes could be formed by inter-
facial polymerization using PSF ultraltration membrane with mo-
lecular weight cut-off (MWCO) 30,000 as support layer. PAMAM-
SiO2 and TMC were used as aqueous and organic monomer
respectively.
2. The better prepared conditions should be controlled as PAMAM
concentration 0.2%, TMC 0.2% and the interfacial polymerization
time should be controlled near 90 s. The addition amount of SiO2
in the system should be nearly 1.01.5% (wt.).
3. The heat stability of resulting PA-SiO2 membrane was enhanced.
The permeation properties had been enhanced for PA-SiO2 NF
membrane without remarkably reducing the rejection rate of salt
solution.
4. The resulting PA-SiO2 is particularly suitable for treating acidic
feeds and salt solution containing bivalent anions. The addition of
SiO2 in the PA membrane improved the anti-fouling ability treating
with raw surface water, which can be a candidate for treating with
surface water.
Acknowledgment
The authors grateful acknowledge the nancial support by the
National Science Foundation (50978068), International Cooperation
Program (Grant: 2010DFA92460), the nancial support by National
High Technology Research and Development Program (863 program,
Grant: 2008AA06Z304). The project was funded by the Research
Fund of Tianjin Key Laboratory of Aquatic Science and Technology
(Grant: TJKLAST-2011-08).
References
[1] M.A. Shannon, P.W. Bohn, M. Elimelech, J.G. Georgiadis, B.J. Marinas, A.M. Mayes,
Science and technology for water purication in the coming decades, Nature 452
(2008) 301310.
[2] C.R. Wu, S.H. Zhang, D.L. Yang, Preparation and performance of novel thermal
stable composite nanoltration membrane, J. Membr. Sci. 326 (2009) 429434.
41
[3] H.C. Song, J.H. Shao, Y.L. He, J. Hou, W.P. Chao, Natural organic matter removal and
ux decline with charged ultraltration and nanoltration membranes, J. Membr.
Sci. 376 (2011) 179187.
[4] A. Caus, S. Vanderhaegen, L. Braeken, B.V. Bruggen, Integrated nanoltration cas-
cades with low salt rejection for complete removal of pesticides in drinkingwater
production, Desalination 241 (2009) 111117.
[5] W.H. Pang, N.Y. Gao, S.J. Xia, Removal of DDT in drinkingwater using
nanoltration process, Desalination 250 (2010) 553556.
[6] S.J. Xia, B.Z. Dong, Q.L. Zhang, B. Xu, N.Y. Gao, C. Causseranda, Study of arsenic
removal by nanoltration and its application in China, Desalination 204 (2007)
374379.
[7] R.S. Harisha, K.M. Hosamani, R.S. Keri, S.K. Nataraj, T.M. Aminabhavi, Arsenic re-
moval from drinkingwater using thin lm composite nanoltration membrane,
Desalination 252 (2010) 7580.
[8] A. Favre-Rguillon, G. Lebuzit, D. Murat, J. Foos, C. Mansour, M. Draye, Selective
removal of dissolved uranium in drinking water by nanoltration, Water Res.
42 (2008) 11601166.
[9] B. Xu, D.P. Li, W. Li, S.J. Xia, Y.L. Lin, C.Y. Hu, C.J. Zhang, N.Y. Gao, Measurements of
dissolved organic nitrogen (DON) in water samples with nanoltration pre-
treatment, Water Res. 44 (2010) 53765384.
[10] B.V. Bruggen, C. Vandecasteele, Removal of pollutants from surface water and
groundwater by nanoltration: overview of possible applications in the drinking
water industry, Environ. Pollut. 122 (2003) 435445.
[11] A.Z. Muhammad, A.W. Mohammad, H. Nidal, Preparation and characterization of
novel porous PMMA-SiO2 hybrid membranes, Desalination 192 (2006) 262270.
[12] C.C. Yang, Y.J. James Li, T.H. Liou, Preparation of novel poly(vinyl alcohol)/SiO2
nanocomposite membranes by a solgel process and their application on alkaline
DMFC, Desalination 276 (2011) 366372.
[13] N. Maximous, G. Nakhla, W. Wong, Preparation, characterization and perfor-
mance of Al2O3/PES membrane for wastewater ltration, J. Membr. Sci. 341
(2009) 6775.
[14] Y.N. Yang, P. Wang, Preparation and characterizations of new PS/TiO2 hybrid
membranes by solgel process, Polymer 47 (2006) 26832688.
[15] A. Bottino, G. Capannelli, V.D. Asti, P. Piaggio, Preparation and properties of novel or-
ganicinorganic porous membranes, Sep. Purif. Technol. 2223 (2001) 269275.
[16] S.J. Oh, N. Kim, Y.T. Lee, Preparation and characterization of PVDF/TiO2 organic
inorganic composite membranes for fouling resistance improvement, J. Membr.
Sci. 345 (2009) 1320.
[17] T.S. Chung, M.L. Chng, K.P. Pramoda, PAMAM dendrimer-induced cross-linking
modication of polyimide membranes, Langmuir 20 (2004) 29662969.
[18] D.A. Tomalia, Starburst dendrimersnanoscopic supermolecules according to
dendritic rules and principles, Macromol. Symp. 101 (1996) 243255.
[19] M.S. Diallo, L. Balogh, A. Shafagati, Poly(amidoamine) dendrimers: a new class of
high capacity chelating agents for Cu(II) ions, Environ. Sci. Technol. 33 (1999)
822824.
[20] L.C. Li, B.G. Wang, H.M. Tan, A novel nanoltration membrane prepared with
PAMAM and TMC by in situ interfacial polymerization on PEK-C ultraltration
membrane, J. Membr. Sci. 269 (2006) 8493.
[21] N.K. Saha, S.V. Joshi, Performance evaluation of thin lm composite polyamide
nanoltration membrane with variation in monomer type, J. Membr. Sci. 342
(2009) 6069.
[22] C.M. Wu, T.W. Xu, W.H. Yang, A new inorganicorganic negatively charged mem-
brane: membrane preparation and characterizations, J. Membr. Sci. 224 (2003)
117125.
[23] T. Kouketsu, S.H. Duan, T. Kai, PAMAM dendrimer composite membrane for CO2
separation: formation of a chitosan gutter layer, J. Membr. Sci. 287 (2007) 5159.
[24] J.N. Shen, H.M. Ruan, L.G. Wu, C.J. Gao, Preparation and characterization of
PESSiO2 organicinorganic composite ultraltration membrane for raw water
pretreatment, Chem. Eng. J. 168 (2011) 12721278.
[25] V. Freger, Kinetics of lm formation by interfacial polycondensation, Langmuir 21
(2005) 18841894.
[26] R. Nadler, S. Srebnik, Molecular simulation of polyamide synthesis by interfacial
polymerization, J. Membr. Sci. 315 (2008) 100105.
[27] Y.J. Song, P. Sun, L.L. Lenry, Mechanisms of structure and performance controlled
thin lm composite membrane formation via interfacial polymerization process,
J. Membr. Sci. 251 (2005) 6779.
[28] D.X. Wang, M. Su, Z.Y. Yu, Separation performance of a nanoltration membrane
inuenced by species and concentration of ions, Desalination 175 (2005) 219225.