Journal of Membrane Science 394395 (2012) 209217

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Journal of Membrane Science

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

High performance ultraltration membrane based on modied chitosan coating

and electrospun nanobrous PVDF scaffolds
Zhiguo Zhao, Jianfen Zheng , Mingji Wang, Haiyuan Zhang, Charles C. Han
Beijing National Laboratory for Molecular Sciences, Joint Laboratory of Polymer Science and Materials, State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry,
Chinese Academy of Sciences, Beijing 100190, China

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

Article history: Liquids ltration technology as one of the paths to sustainable water use is getting more and more
Received 22 September 2011 attention. A new type of high ux ultraltration (UF) or nanoltration medium based on electrospun
Received in revised form brous scaffold and ultrathin top barrier layer was fabricated recently. Based on this new method, the
30 November 2011
chitosan (CTS) which is one of the best top layer materials due to its hydrophilicity and high water-
Accepted 28 December 2011
permeability was coupled with electrospun polyvinylidene uoride (PVDF) nanobers to compose a new
Available online 3 January 2012
type UF membrane. In this work, the chitosan was crosslinked and modied by glutaraldehyde (GA)
and terephthaloyl chloride (TPC) to adjust its water resistance and surface properties. The modied
Keywords:
Chitosan
membrane was characterized by FTIR, SEM, UV-spectra, static water contact angle analysis and ltration
Nanobers test. The modied membrane gets broader operating environment range and keeps a good ux rate and
Modication rejection efciency in bovine serum albumin (BSA) ltration tests at 0.2 MPa, about 70.5 L/m2 h, rejection
Ultraltration efciency >98% which are higher than that of 57.1 L/m2 h, rejection efciency98% of the commercial UF
membranes, while the fouling of the membrane was kept at a very low level. This work may provide a
practical possibility to the water ltration industry.
2012 Elsevier B.V. All rights reserved.

1. Introduction membranes [311]. Currently, much effort is being devoted to

The worldwide problems associated with the shortage of clean,
fresh water have attracted more and more attention. Liquid ltra-
tion technique was discovered in 19th century, just as diffusion,
dialysis and osmosis [1,2], and became well developed in the
20th century. Liquid ltration membrane such as micro-, ultra-
and nano-ltration membranes and even reverse osmosis mem-
branes were invented and their markets spread rapidly throughout
the world. As one of the most important technical methods for
potable water purication and biomaterials concentration, ultra-
ltration played an important role and took a signicant portion
of worldwide market. Solgel liquid ltration was the rst genera-
tion ultraltration membrane [1], and with the great development
of engineering plastics, new types of ultraltration membranes
were invented, mostly as asymmetric membranes at present,
such as polysulfone, polyvinylidene uoride and polyacrylonitrile
Abbreviations: UF, ultraltration; CTS, chitosan; PVDF, polyvinylidene uoride;
GA, glutaraldehyde; TPC, terephthaloyl chloride; BSA, bovine serum albumin; NFCM,
nanobrous composite membrane.
Corresponding author. Tel.: +86 10 82618089; fax: +86 10 62521519.
Corresponding author. Tel.: +86 10 62550093; fax: +86 10 62521519.
E-mail addresses: zhengjianf@iccas.ac.cn (J. Zheng), c.c.han@iccas.ac.cn
(C.C. Han).
improve the membrane performance in terms of ux rate, anti-
fouling property, chemical resistance, etc. [2,1215].
Meanwhile, the non-woven ber industry has made a rapid
development recently. Traditionally, wet-laid, melt-blown and
spun-bonded non-woven articles were well and vastly produced.
In addition, the electro-spinning as a new non-woven technique
that creates sub-micron to nano scale bers through an electrically
charged jet of polymer solution/melt, has gained greatly increasing
appeal [1619].
Compared with the traditional non-woven articles (such as wet-
laid and melt-blown non-woven article), electrospun bers have
much smaller diameter, usually 10100 times thinner than the
former. Consequently, the electrospun nanobrous articles pos-
sess some attractive attributes, such as high porosity, wide pore
size range, interconnected open pore structure, a large surface
area per unit volume, high exibility, good biocompatibility and
biodegradability (for bers of biomaterials) and good modiabil-
ity. With these advantages, the electrospun nanobers have been
demonstrated in many applications, such as optical and chem-
ical sensors [2022], photovoltaics cells [23], protective textiles
[2426], wound dressing and as scaffolds in tissue engineering
[2731], immobilized enzymes and catalyst system [32], and l-
tration materials [3336].
The nanobrous membranes were rst successfully used in
air ltrations, and then directly used as liquid macro-ltration

0376-7388/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2011.12.043
210 Z. Zhao et al. / Journal of Membrane Science 394395 (2012) 209217
media [34]. In 2005, the electrospun nanobers and liquid
ltration were organically tied together by Ben Chus group [37].
In their work, composite membranes were prepared with elec-
trospun PAN nanobers as the scaffold and chitosan as the top
ultrathin barrier layer. For the wateroil solution as the feeding liq-
uid, the nanobrous composite membranes obtained an excellent
ux rate at high rejection efciency of >99%. With their precursor
work, a lot of excellent works were carried out, such as crosslink-
ing PVA and cellulose acetate on the scaffolds of PAN electrospun
nanobers [38,39], and surface polymerization of polyamide on the
electrospun nanobrous scaffolds of PAN [40].
Chitosan, poly[-(1,4)-2-amino-2-deoxy-d-glucose], has good
water permeability and antifouling abilities. However, its high
swelling property in water makes it imperfect in some ltration
environment. Protein ltration for example, the original chitosan
coating barrier on the electrospun nanobers gives less efciency
compared with that for oilwater ltration. So, the modication
of the chitosan is necessary to enhance its scope of application.
The modication of chitosan has been studied by many scien-
tic groups; glutaraldehyde (GA), lactic acid, maleic anhydride,
etc. were used as the modication regent [4144]. In this work,
GA was used to moderate bulk-crosslink rstly, and subsequently
terephthaloyl chloride (TPC) was used to crosslink the surface of
the chitosan barrier.
When the CTS was crosslinked and the amino group was reacted,
the thin lm of chitosan can achieve distinct advantages for water
ltration: rst, dramatic water swelling decreased, so it could stand
high pressure in ltration tests and keep lm morphology well.
Second, the electric charge was normalized, and thus reduced the
interaction between chitosan and protein, so the protein adsorption
became low. Third, the range of pH environment for chitosan was
expanded: the membrane could function well at a high efciency,
in both acidic and basic environment.
2. Experimental
2.1. Materials and preparation
Polyvinylidene uoride (PVDF) with a weight average molecu-
lar weight (Mw) of about 37 104 g/mol and terephthaloyl chloride
(TPC) were purchased from Aldrich Chemicals. Chitosan (high
viscosity, Mw 40 104 g/mol) with about 80% deacetylate was
purchased from Fluke Aldrich Chemical. No-woven PET article
was supplied by Guocheng CO. (Wuxi, China). Glutaraldehyde
(GA), triethylamine, N,N-dimethyl formamide (DMF), acetic acid,
1,2,4,5-benzenetetracarboxylic anhydride, tetrahydrofuran (THF),
and bovine serum albumin (BSA) were purchased from Beijing
Chem. Co. (Beijing, China). And other reagents involved in this work
with no special descriptions were used directly without further
purication.
Chitosan was necessarily puried before use by the following
procedure. A certain amount of chitosan sample was dissolved in
dilute acetic acid (1%, v/v) to form 1 wt% chitosan solution and the
solution was ltered using a sintered glass lter to remove insol-
uble substance. Subsequently, the solution was casted into a large
glass Petri dish and left in the fume-hood for about 23 days to dry.
The dried chitosan lm was soaked in sodium hydroxide solution
(1 mol/L) for several hours to remove the residual acetic acid. Then
the double distilled water was used to wash the lm several times
until it was totally neutralized. The neutralized lm was freeze-
dried at last. The puried chitosan sample was dissolved in dilute
acetic acid solution (1%, v/v) to prepare the casting solution at the
concentration ranging from 0.6 to 1.0 mg/ml.
Triethylamine needs to be redistilled to remove the rst and the
second amine which will have erce side reaction with the chloride
groups. The original triethylamine reagent was mixed with a
certain amount, about 5 g/100 ml, of 1,2,4,5-
benzenetetracarboxylic anhydride with a mild stirring, and
redistilled at 90 C gently. The distillation was stored in conical
beaker at cool and dry place to avoid the humidity and the sunlight.
2.2. Electrospinning
PVDF could be Electrospun easily and efciently based on some
previous work in our group [45]. PVDF was dissolved in mixed
solution of N,N-dimethyl formamide (DMF) and acetone, at differ-
ent concentration range from 14 wt% to 24 wt%, with the ratio of
DMF/acetone at 3/7, 4/6, 5/5, 6/4 and 7/3 at 50 C with gentle stirring
for 24 h or a sufciently long period of time to form the homogenous
state. The PVDF solution was directly electrospun onto the surface
of non-woven PET micro-lter substrate at 1518 kV through an
electrospinning device. The tip-to-collector distance was 15 cm and
the electrospinning temperature including polymer solution and
the environment was controlled at 50 2 C. The solution was fed
at a rate of 50 l/min from a 5 ml syringe with a capillary tip which
has an inner diameter of 0.3 mm.
With the change of the mixed solvent and the concentration,
the morphology and the diameter of the PVDF nanobers was well
controlled. To make the nanobrous article smoother and denser,
gentle hot-pressing process was executed, at 100 C and 5000 Pa for
2 h. The amount of PVDF nanobers spun per unit area was about
1.21.5 mg/cm2 .
2.3. Chitosan coating and modication
2.3.1. Initial chitosan coating
The composite brous support containing PVDF nanobers and
non-woven PET substrate was placed onto the plate of a stepped
coaterR [46]. Certain amount of the chitosan casting solution, the
concentration of which ranged from 0.6 wt% to 1.0 wt%, was applied
into the space between casting-knife and composite brous sup-
port. Specic casting speed, 5 mm/s, and constant temperature of
25 C was applied. The three-tier composite membrane was dried
for at least 24 h at 50 C in the blast drying oven. The dried mem-
brane was then washed with double distilled water several times
to make sure it completely neutralized and dried the second time
under ambient condition.
2.3.2. Chitosan crosslinking with GA
The amount of monomers in the chitosan solution was rst cal-
culated, and then different amount of GA was added into the casting
solution. The R represents the ratio of the amount of crosslinking
functional groups in the added GA reagent and the chitosan solu-
tion according to the Schiff Base Imine Functionality [42]. And then
the mixture was stirred and dispersed under ultrasonic for 5 min to
form homogenous solution. Coating process of the three-tier com-
posite membrane with cross-linking reagent (GA) was the same as
the initial chitosan coating. The three-tier composite membrane
was dried at 60 C in the drying oven and then 100 C for additional
3 h to stabilize the crosslinking between chitosan and GA.
2.3.3. Chitosan modication with TPC
The experiment was carried out in the dry box (relative humidity
<30%). THF, 20 ml at 0 C, was lled into 100 ml beaker. The for-
mer three-tier original CTS composite membrane with the size of
4 cm 4 cm in square was immersed into the THF solvent. Then 2 ml
of cold triethylamine was added into the beaker to form an alkaline
environment. And then, 2 ml TPC solution, 5 wt% in THF solvent, at
0 C, was slowly added into the beaker drop by drop under a mild
stirring. The whole beaker was sealed up and kept for 72 h at 0 C.
The modied membrane was washed with THF, 1 M NaOH and 1 M
 Z. Zhao et al. / Journal of Membrane Science 394395 (2012) 209217
HCl subsequently for 3 times, and then double distilled water for
several times and dried in ambient condition.
2.3.4. Chitosan co-modication with GA and TPC
First the chitosan was crosslinked with GA to form a bulk
crosslinked chitosan, and then the surface of the chitosan was
modied with TPC. The whole process was carried out precisely
in accordance to the separate process mentioned above.
2.4. Characterization
The viscosity of the chitosan casting solution was measured
with SNB-1 digital viscosity meter (NiRun Co., Shanghai, China) at
a constant temperature of 25 C.
The morphologies of the electrospun bers and the composited
membranes were observed using scanning electron microscope
(SEM, JEOL JSM-6700F, Japan), at an accelerating voltage of 5 kV.
Each sample was sputter-coated with platinum for analysis.
The virgin chitosan and the modied chitosan were tested by
FTIR-ATR mode on an infrared spectrometer (IR, BRUKER TEN-
SOR27, Germany) in the range of 4000600 cm1 .
The hydrophilicity performance of the membranes was eval-
uated on static water contact angle measurement instrument
(PowerEach Co., Shanghai, China).
The water uptake property was determined gravimetrically. The
completely neutralized and dried chitosan and GA crosslinked chi-
tosan dense lms, about 20 m thick, were weighted directly on
the electronic balance (METTLER TOLEDO AL204). Then the samples
were introduced into beakers containing 20 ml of swelling medium
and shaken at 25 C. Every 30 min the lms were removed from
the medium, blotted off the water on the surface and immediately
weighted. This procedure was repeated until the lms reached con-
stant weight (equilibrium water uptake). The water uptake (Wu ) of
the lms was calculated according to the following equation:
Wc W0
Wu (%) = 100,
W0
where W0 and Wc are the weights of the samples in the dry and
swollen states, respectively.
2.5. Filtration performance test
Bovine serum albumin was separately dissolved in four types
of solvent: ultra-pure water and three different buffers, pHs 3, 6,
and 9 (1% acetate acid, phosphate buffered saline and borax salt
dissolved in ultra-pure water). Also these four different solvents
were prepared as feed solution for ultraltration process. A series
of BSA aqueous solution was detected by ultravioletvisible (UV)
spectroscopy at a wavelength of 280 nm. Standard UV absorption
curve of BSA was plotted by varying concentrations of the initial
BSA feed solutions, by which the concentration of ltrate solution
was determined. The rejection percentage was calculated by using
the following equation:
Cf Cp
Rejection (%) = 100,
Cf
where Cf and Cp represent the BSA concentration of the feed solu-
tion and that of the ltrate solution, respectively.
The three-tier composite membranes were tested on an ultral-
tration cup at a constant pressure of 0.2 MPa, an effective ltration
area of 13.4 cm2 , a constant temperature of 25 C and a stirring rate
of 300 rpm. A 10 min pre-compacted process with pure water l-
tration at 0.2 MPa was carried out for each membrane. The BSA
concentration of 1 g/L was used, with different types of solvents,
including pure water, pH 7 buffer, pH 9 buffer and 1%HAc aqueous
solution (pure water as blank test was operated as well). And the
211
ltration data involved in this work with no special descriptions
were all obtained under the same conditions.
Three membrane specimens were tested and the nal results
were averaged. The commercial UF membrane (Sepro UF, PES10)
was tested for comparison.
3. Result and discussion
3.1. Electrospinning of PVDF
PVDF nanobers were successfully fabricated in the laboratory.
Fig. 1 showed the morphology of the electrospun PVDF nanobers.
The series of SEM photographs demonstrated that with the increase
of the concentration of the PVDF, the diameter of the ber increases;
meanwhile, with the increase of the ratio of acetone in the mixed
solvent, the diameter of the ber increase greatly as well. Ignore
some usual factors in the process, for example, conductivity, elec-
tric charge property and surface energy, the dominating factor in
this process was that, with the speed-up of the solvent evaporation
rate, the solidication rate of the polymer was speeded up as well,
as a result, the diameter of the bers increased. The more uniform
and thinner the bers are, the higher operating pressure the top
layer could withstand for ltration process. Therefore, the fabrica-
tion condition were chosen at the 16 wt% polymer concentration
with the ratio of DMF/acetone = 7/3 and the average diameter of
the PVDF nanobers is about 170 nm.
3.2. Preparation of three-tier composite membrane
Viscosity of the casting solution was one of the key parameters
for the casting process. The thickness of the top layer of CTS ranges
from 200 nm to 800 nm with the change of the concentration of the
casting solution from 0.6% to 1.0% (shown in Table 1). At the con-
centration of 0.5 wt%, a awless CTS layer can hardly be obtained.
Fig. 2 showed the morphology of the three-tier composite mem-
branes with a concentration of casting solution of 0.6 wt%. The SEM
images of CTS and modied CTS composite membrane showed little
difference. The smooth top layer surface was kept well after mod-
ication and the thickness of the casting CTS layer was uniform.
The thickness of the top barrier layer is one of the most impor-
tant parameter for the nal performance. With the prerequisite of
enough mechanical strength, the thinner the top layer is the better
the performance will be.
3.3. Modication of CTS with GA and TPC
The natural polysaccharideschitosan, has a lot of amine groups
which is quite reactive with other groups, for example acyl halides,
aldehyde, peroxide and epoxy. The mechanism of the reactions in
this work between GA&CTS and TPC&CTS is shown in Figs. 3 and 4.
The former is based on Schiff Base Imine Functionality or Michael-
type Adducts with Terminal Aldehydes and the latter is based on
electrophilic substitution reaction.
Crosslinking chitosan with GA is a general method which has
been studied by many research groups [41,42]. Fig. 5 showed the
results of FTIR-ATR spectra of the virgin CTS samples, the sam-
ples after crosslinking with GA (CTS-GA) and the samples after
crosslinking with TPC (CTS-TPC). The virgin CTS spectrum showed
the majority of the function groups: the superposition peak of
OH and NH2 band at 34003200 cm1 , C H stretching band at
28702920 cm1 , the bridge oxygen stretching band at 1160 cm1 ,
and the C O stretching bands at 1070 cm1 and 1030 cm1 . The chi-
tosan used in this work has an average degree of deacetylation of
80%, so that, the peaks at 1640 cm1 and 1550 cm1 were formed by
the co-contribution of the residual acetamide groups bands which
212 Z. Zhao et al. / Journal of Membrane Science 394395 (2012) 209217

Fig. 1. The morphology of the electrospun PVDF nanobers obtained from different PVDF concentrations and different solvent compositions: (A) 14 wt%, 5/5; (B) 18 wt%,
5/5; (C) 20 wt%, 5/5; (D) 24 wt%, 5/5; (E) 16 wt%, 7/3; (F) 16 wt%, 6/4; (G) 16 wt%, 4/6; (H) 16 wt%, 3/7*. *The ratio of DMF/acetone by v/v.

Table 1
The viscosity of the chitosan casting solution with different concentration and the thickness of corresponding casting chitosan layer.

Concentration 0.5% 0.6% 0.7% 0.8% 0.9% 1.0%

Viscosity (mPa s) 115 188 224 338 450 571

Thickness of casting layer (nm) 200 35 320 45 450 60 600 80 800 150
 Z. Zhao et al. / Journal of Membrane Science 394395 (2012) 209217
Fig. 2. The morphology of the composite membrane. (A) CTS layer; (B) GA crosslinked CTS layer (CTS-GA); (C) TPC modied CTS layer (CTS-TPC); (D) the cross section of the
CTS coating three-tier composite membrane. The concentration of the casting solution is 0.6 wt% (inset: enlarged image of the top layer).
are located from 1660 cm1 to 1500 cm1 , and the NH2 bending
band which is broad and centred near 1585 cm1 .
As a result of crosslinking reaction, signicant changes were
observed in the FTIR-ATR spectrum of the crosslinked samples
versus the virgin CTS. The new peak at 1720 cm1 and 1450 cm1
indicated the presence of a carbonyl groups and CH2 groups,
respectively. And at the carbonyl-amide region, because of the
depletion of the NH2 , the corresponding broad band which
is centred near 1585 cm1 , together with the appearance of
the new peak for C N, which can be located anywhere from
1620 cm1 to 1660 cm1 according to the literature [41,42], the
peak at 1640 cm1 was strengthened and meanwhile the peak at
1550 cm1 was weakened.
Modication of CTS with TPC is a novel method to modify the
surface of the CTS ultra-thin barrier. At the alkaline condition, elec-
trophilic reagents, acyl chloride was attacked by the nucleophilic
reagent, amino groups, and formed the carbonyl-amide groups. The
rise at 1590 cm1 and 1450 cm1 indicated the introduction of the
benzene ring whose peaks are located at 1600 cm1 ,1580 cm1 , and
1450 cm1 all of which became stronger especially while the ring
is connected with the C O group due to the conjugation effect.
Also the peak at 870 cm1 of C H band in benzene ring as the cor-
roborative evidence could be observed at the ngerprint region.
The change of the spectrum band from 1700 cm1 to 1500 cm1
was inuenced by two simultaneous factors. One was the disap-
pearance of the NH2 , which inuence a broad range centred near
1585 cm1 , to reduce the absorption. While the other one was the
appearance of aromatic amide, whose peaks located at 1650 cm1
and 1550 cm1 , to raise the absorption. And the former was the
dominant factor, so the peaks were weakened. Furthermore, no
peaks were obtained at the range from 1700 cm1 to 1800 cm1 ,
which indicated that neither ester groups were generated nor resid-
ual acyl halides retained.
213
The four types of CTS: virgin CTS, GA crosslinked CTS, TPC mod-
ied CTS and GA, TPC co-modied CTS were subjected to the static
water contact angle measurement. The results in Fig. 6 showed
that, even though the amine groups were reacted, the hydroxyl
group survived and kept the barrier layer with excellent hydrophilic
nature which is very important for anti-fouling property of the
ultraltration membranes.
3.4. The ltration performance of the composite membranes
Fig. 7 showed the performance of virgin CTS coated compos-
ite membranes. Take CTS-1% for example, the low BSA rejection
exposed the low effectiveness of the virgin CTS barrier. Due to
the penetration of BSA into the barrier, the water ux became
extremely lowered. The thicker the CTS barrier was, the higher
BSA rejection and lower water ux were obtained. The inuence
of the pH condition of the feed solution was also evaluated. Table 2
showed the different water ux and BSA rejection of the CTS-1%
and CTS-0.6% composite membrane. At pHs 9 and 7, no obvious
change was obtained, while at pH 3 (1% acetic acid), at the very
beginning of the ltration test, the water ux became higher and
the BSA rejection get lower oppositely. After a period of ltration,
about 45 h, the CTS barrier layer was totally destroyed, and the
BSA solution passed through the membrane directly. The reason is
that, in the acetous condition, the CTS became more swollen; the
potential gaps for water ow through became more possible and
thus caused to the poor performance. As time goes on the CTS layer
was gradually dissolved, and destroyed at last.
For the purpose of obtaining high ux and BSA rejection
efciency and also obtaining acid resistance simultaneously, a mod-
ied process was carried out.
First, CTS was crosslinked with GA. The water uptake property of
the CTS casting lms varied with the crosslinking ratio (R), as shown
214 Z. Zhao et al. / Journal of Membrane Science 394395 (2012) 209217

Fig. 3. Chitosan crosslinked with GA: Schiff Base Imine Functionality (left) and/or Michael-type Adducts with Terminal Aldehydes (right).

Fig. 4. The amidation of the CTS with TPC.

Fig. 5. FTIR-ATR spectrum of virgin CTS, GA crosslinked CTS (CTS-GA) and TPC modied CTS (CTS-TPC).
 Z. Zhao et al. / Journal of Membrane Science 394395 (2012) 209217 215

Fig. 6. Static water contact angle measurement to membranes of virgin, GA crosslinked, TPC modied, and GA, TPC co-modied CTS.

Fig. 7. Filtration test of virgin CTS coated NFCMs.
in Table 3. The results indicated that, the CTS obtained less water
swelling property and good acid resistance after GA crosslinking.
Meanwhile, the performance of the GA modied CTS-0.6% coated
nanobrous composite membrane (NFCM) was shown in Fig. 8. The
membrane CTS-0.6% has the thinnest barrier layer and the highest
ux for water ltration, so it is the best choice for the modica-
tion. When the crosslink ratio R 1, the crosslinked CTS barrier
layer became too fragile to work, so there is no data for R 1. The
results showed that, after the crosslinking, the membranes get a lit-
tle increase in rejection efciency of BSA, and decrease in ux rate
simultaneously. The ltration test showed the consistent results
with the water uptake test. The reason is obviously that, because
of the form of crosslinked network, the CTS barrier layer became
denser and less water swelling.
At the ratio R = 1, the crosslinked CTS barrier becomes too fragile
to work under pressure, and meanwhile at the ratio R = 1/10, the
effect of crosslinking was not enough. So the middle case at the
ratio R = 1/3 was selected.
Second, the CTS barrier was modied by TPC. Long modication
time, about 72 h, was taken to make sure the surface modication
Fig. 8. Filtration test of GA crosslinked CTS-0.6% coated NFCMs: R = 0, R = 1/10 and
R = 1/3.
reaction completed at a high ratio. The CTS-0.6% was the main
choice because it has visibly high ux. The ltration performance
of TPC modied CTS coated NFCM was evaluated at the same time.
After the surface modication, the BSA became more difcult to
pass through the barrier layer, so the high rejection efciency was
obtained. The results of water ux rate at 71.4 L/m2 h, and BSA
rejection at 98% (shown in Table 4), was very satisable.
The modication reagent GA was added into the solution of CTS
to form homogeneous solution. With the water solvent evaporat-
ing, both the CTS and GA became concentrated, and at last the CTS
was crosslinked with GA at the bulk level. While the modication
regent TPC was added into THF environment with chitosan mem-
brane immersed. Chitosan solid surface was wettable with THF and
after the reaction between CTS and TPC, the top surface of CTS
barrier became denser. The former modication reaction mainly
occurred in the bulk of chitosan, while the latter occurred at the top
surface. So the ltration results shown in Table 4 were different.

Table 2
PH inuence of the CTS-1% and CTS-0.6% membranes.

Sample H2 O BSA in pure water BSA in pH 9 buffer BSA in pH 7 buffer BSA in 1%HAc buffer
2 2 2 2
Flux (L/m h) Rej ratio Flux (L/m h) Rej ratio (%) Flux (L/m h) Rej ratio (%) Flux (L/m h) Rej ratio (%) Flux (L/m2 h) Rej ratio (%)
(%)

CTS-1% 20.0 1.5 14.8 0.8 85.2 1.0 13.8 0.7 86.4 0.9 13.8 0.7 85.7 0.9 16.2 0.9 80.3 1.1
CTS-0.6% 204.8 8.2 128.6 6.4 19.2 3.5 119 5.9 20.4 2.7 123.8 6.1 20.1 2.7 161.9 8.0 12.7 3.7

Table 3
The water uptake of dense CTS lms and CTS-GA lms: R = 1/10, R = 1/3, and R = 1/1.

Sample CTS CTS-GA 1/10 CTS-GA1/3 CTS-GA1/1

Wu in deionized water (%) 157 11 115 9 67 7 31 3

Wu in 1%HAc buffer (%) Dissolved 126 7 71 5 32 3
216 Z. Zhao et al. / Journal of Membrane Science 394395 (2012) 209217

Table 4
Filtration test of the CTS-0.6%, CTS-0.6%-GA, CTS-0.6%-TPC and CTS-0.6%-GA-TPC.

Sample H2 O BSA in pure water BSA in pH 9 buffer BSA in pH 7 buffer BSA in 1%HAc buffer

Flux (L/m2 h) Rej ratio Flux (L/m2 h) Rej ratio (%) Flux (L/m2 h) Rej ratio (%) Flux (L/m2 h) Rej ratio (%) Flux (L/m2 h) Rej ratio (%)
(%)

CTS-0.6% 204.8 8.2 128.6 6.4 19.2 3.5 119.0 5.9 20.4 2.7 123.8 6.1 20.1 2.7 161.9 8.0 12.7 3.7
CTS-0.6%-GA 181.0 8.0 114.3 5.7 33.4 2.1 109.5 5.4 36.7 1.9 109.5 5.3 35.4 2.3 114.3 5.8 30.8 2.1
CTS-0.6%-TPC 101.0 4.4 71.4 3.5 98.5 0.2 69.3 3.1 98.8 0.1 70.5 3.2 98.7 0.2 73.0 3.67 96.7 0.2
CTS-0.6%-GA-TPC 72.7 3.6 70.5 3.4 98.9 0.2 68.6 3.2 99.1 0.1 70.0 3.4 99.3 0.1 71.0 3.5 98.7 0.2

To evaluate the acid resistance property directly, the CTS and
GA crosslinked CTS coated membranes were immersed into 1%HAc
solution, and subjected to ultrasound treatment for at least 1 h, and
the CTS-GA membrane kept the original morphology well while vir-
gin CTS coated membranes was soon totally destroyed. Also the TPC
modied CTS coated membranes were immersed into 1%HAc solu-
tion, and subjected to the same ultrasound treatment. Relied only
on the top surface crosslinking, the membranes could not with-
stand the treatment for more than 5 min.
The most important advantage for GA crosslinking is the acqui-
sition of acid resistance property for the CTS barrier layer which
makes the membrane to withstand the operation under the acid
environment. While the most important advantage for TPC modi-
cation is the increase of surface crosslinking density and greatly
increased BSA rejection efciency. So with the combination of the
two steps of modication, high performance membrane with both
acid resistance and high BSA rejection efciency was obtained.
The nal performance of the GA and TPC co-modied CTS coated
NFCM is 70.5 L/m2 h at the BSA rejection of 98.9%, compared with
the commercial UF membrane (Sepro UF, PES10), 57.1 L/m2 h, 98%
BSA rejection, the performance is enhanced for more than 20%.
Long period performance of the antifouling property is also
evaluated. The results were shown in Fig. 9. Take three types of
membrane: CTS-1% coated membrane, GA-TPC co-modied CTS-
0.6% coated membrane and the commercial membrane, of which
the BSA rejection efciency of both the latter two are all over
than 98%. After 24 h operation, the efciency of CTS-0.6%-GA-TPC
NFCM decrease from 70.5 to 65.6 L/m2 h, while virgin CTS-1% from
14.8 to 8.32 L/m2 h and commercial UF from 57.1 to 37.8 L/m2 h.
The result revealed that the modied CTS-0.6%-GA-TPC membrane
showed very good antifouling property: after working 24 h, the ux
decreased less than 7%.
Fig. 9. The performance of each membrane for long period of operation.
4. Conclusion
The CTS coated, based on nanobrous PVDF scaffold composite
ultraltration membrane was successfully fabricated and a novel
method to modify by GA and TPC was successfully carried out.
With the two steps modication, the top barrier layer of chitosan on
the scaffolds of electrospun PVDF nanobers provided an excellent
performance in the water-protein liquid ltration. The thin-lm
composite nanobrous ultraltration membrane gave a result of
70.5 L/m2 h of ux, and 98.9% of BSA rejection, at 0.2 MPa. Compared
with the commercial UF membrane (Sepro UF, PES10), 57.1 L/m2 h
and 98%, the ltration efciency was enhanced about 25% at a
very high rejection efciency level. And the membrane showed a
very good antifouling property that after 24 h of operation, the ux
decreased for less than 7%. This work may provide a new direction
for ltration applications.
Acknowledgements
This work was nancially supported by Main Direction Pro-
gram of Knowledge Innovation of Chinese Academy of Sciences
(KJCX2-YW-H19) and National Natural Science Foundation of China
(20904060).
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