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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


improve the membrane performance in terms of ux rate, anti-
The worldwide problems associated with the shortage of clean, fouling property, chemical resistance, etc. [2,1215].
fresh water have attracted more and more attention. Liquid ltra- Meanwhile, the non-woven ber industry has made a rapid
tion technique was discovered in 19th century, just as diffusion, development recently. Traditionally, wet-laid, melt-blown and
dialysis and osmosis [1,2], and became well developed in the spun-bonded non-woven articles were well and vastly produced.
20th century. Liquid ltration membrane such as micro-, ultra- In addition, the electro-spinning as a new non-woven technique
and nano-ltration membranes and even reverse osmosis mem- that creates sub-micron to nano scale bers through an electrically
branes were invented and their markets spread rapidly throughout charged jet of polymer solution/melt, has gained greatly increasing
the world. As one of the most important technical methods for appeal [1619].
potable water purication and biomaterials concentration, ultra- Compared with the traditional non-woven articles (such as wet-
ltration played an important role and took a signicant portion laid and melt-blown non-woven article), electrospun bers have
of worldwide market. Solgel liquid ltration was the rst genera- much smaller diameter, usually 10100 times thinner than the
tion ultraltration membrane [1], and with the great development former. Consequently, the electrospun nanobrous articles pos-
of engineering plastics, new types of ultraltration membranes sess some attractive attributes, such as high porosity, wide pore
were invented, mostly as asymmetric membranes at present, size range, interconnected open pore structure, a large surface
such as polysulfone, polyvinylidene uoride and polyacrylonitrile 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-
Abbreviations: UF, ultraltration; CTS, chitosan; PVDF, polyvinylidene uoride; ical sensors [2022], photovoltaics cells [23], protective textiles
GA, glutaraldehyde; TPC, terephthaloyl chloride; BSA, bovine serum albumin; NFCM, [2426], wound dressing and as scaffolds in tissue engineering
nanobrous composite membrane. [2731], immobilized enzymes and catalyst system [32], and l-
Corresponding author. Tel.: +86 10 82618089; fax: +86 10 62521519.
Corresponding author. Tel.: +86 10 62550093; fax: +86 10 62521519. tration materials [3336].
E-mail addresses: zhengjianf@iccas.ac.cn (J. Zheng), c.c.han@iccas.ac.cn The nanobrous membranes were rst successfully used in
(C.C. Han). 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 groups. The original triethylamine reagent was mixed with a
ltration were organically tied together by Ben Chus group [37]. certain amount, about 5 g/100 ml, of 1,2,4,5-
In their work, composite membranes were prepared with elec- benzenetetracarboxylic anhydride with a mild stirring, and
trospun PAN nanobers as the scaffold and chitosan as the top redistilled at 90 C gently. The distillation was stored in conical
ultrathin barrier layer. For the wateroil solution as the feeding liq- beaker at cool and dry place to avoid the humidity and the sunlight.
uid, the nanobrous composite membranes obtained an excellent
ux rate at high rejection efciency of >99%. With their precursor 2.2. Electrospinning
work, a lot of excellent works were carried out, such as crosslink-
ing PVA and cellulose acetate on the scaffolds of PAN electrospun PVDF could be Electrospun easily and efciently based on some
nanobers [38,39], and surface polymerization of polyamide on the previous work in our group [45]. PVDF was dissolved in mixed
electrospun nanobrous scaffolds of PAN [40]. solution of N,N-dimethyl formamide (DMF) and acetone, at differ-
Chitosan, poly[-(1,4)-2-amino-2-deoxy-d-glucose], has good ent concentration range from 14 wt% to 24 wt%, with the ratio of
water permeability and antifouling abilities. However, its high DMF/acetone at 3/7, 4/6, 5/5, 6/4 and 7/3 at 50 C with gentle stirring
swelling property in water makes it imperfect in some ltration for 24 h or a sufciently long period of time to form the homogenous
environment. Protein ltration for example, the original chitosan state. The PVDF solution was directly electrospun onto the surface
coating barrier on the electrospun nanobers gives less efciency of non-woven PET micro-lter substrate at 1518 kV through an
compared with that for oilwater ltration. So, the modication electrospinning device. The tip-to-collector distance was 15 cm and
of the chitosan is necessary to enhance its scope of application. the electrospinning temperature including polymer solution and
The modication of chitosan has been studied by many scien- the environment was controlled at 50 2 C. The solution was fed
tic groups; glutaraldehyde (GA), lactic acid, maleic anhydride, at a rate of 50 l/min from a 5 ml syringe with a capillary tip which
etc. were used as the modication regent [4144]. In this work, has an inner diameter of 0.3 mm.
GA was used to moderate bulk-crosslink rstly, and subsequently With the change of the mixed solvent and the concentration,
terephthaloyl chloride (TPC) was used to crosslink the surface of the morphology and the diameter of the PVDF nanobers was well
the chitosan barrier. controlled. To make the nanobrous article smoother and denser,
When the CTS was crosslinked and the amino group was reacted, gentle hot-pressing process was executed, at 100 C and 5000 Pa for
the thin lm of chitosan can achieve distinct advantages for water 2 h. The amount of PVDF nanobers spun per unit area was about
ltration: rst, dramatic water swelling decreased, so it could stand 1.21.5 mg/cm2 .
high pressure in ltration tests and keep lm morphology well.
Second, the electric charge was normalized, and thus reduced the 2.3. Chitosan coating and modication
interaction between chitosan and protein, so the protein adsorption
became low. Third, the range of pH environment for chitosan was 2.3.1. Initial chitosan coating
expanded: the membrane could function well at a high efciency, The composite brous support containing PVDF nanobers and
in both acidic and basic environment. 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
2. Experimental into the space between casting-knife and composite brous sup-
port. Specic casting speed, 5 mm/s, and constant temperature of
2.1. Materials and preparation 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-
Polyvinylidene uoride (PVDF) with a weight average molecu- brane was then washed with double distilled water several times
lar weight (Mw) of about 37 104 g/mol and terephthaloyl chloride to make sure it completely neutralized and dried the second time
(TPC) were purchased from Aldrich Chemicals. Chitosan (high under ambient condition.
viscosity, Mw 40 104 g/mol) with about 80% deacetylate was
purchased from Fluke Aldrich Chemical. No-woven PET article 2.3.2. Chitosan crosslinking with GA
was supplied by Guocheng CO. (Wuxi, China). Glutaraldehyde The amount of monomers in the chitosan solution was rst cal-
(GA), triethylamine, N,N-dimethyl formamide (DMF), acetic acid, culated, and then different amount of GA was added into the casting
1,2,4,5-benzenetetracarboxylic anhydride, tetrahydrofuran (THF), solution. The R represents the ratio of the amount of crosslinking
and bovine serum albumin (BSA) were purchased from Beijing functional groups in the added GA reagent and the chitosan solu-
Chem. Co. (Beijing, China). And other reagents involved in this work tion according to the Schiff Base Imine Functionality [42]. And then
with no special descriptions were used directly without further the mixture was stirred and dispersed under ultrasonic for 5 min to
purication. form homogenous solution. Coating process of the three-tier com-
Chitosan was necessarily puried before use by the following posite membrane with cross-linking reagent (GA) was the same as
procedure. A certain amount of chitosan sample was dissolved in the initial chitosan coating. The three-tier composite membrane
dilute acetic acid (1%, v/v) to form 1 wt% chitosan solution and the was dried at 60 C in the drying oven and then 100 C for additional
solution was ltered using a sintered glass lter to remove insol- 3 h to stabilize the crosslinking between chitosan and GA.
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. 2.3.3. Chitosan modication with TPC
The dried chitosan lm was soaked in sodium hydroxide solution The experiment was carried out in the dry box (relative humidity
(1 mol/L) for several hours to remove the residual acetic acid. Then <30%). THF, 20 ml at 0 C, was lled into 100 ml beaker. The for-
the double distilled water was used to wash the lm several times mer three-tier original CTS composite membrane with the size of
until it was totally neutralized. The neutralized lm was freeze- 4 cm 4 cm in square was immersed into the THF solvent. Then 2 ml
dried at last. The puried chitosan sample was dissolved in dilute of cold triethylamine was added into the beaker to form an alkaline
acetic acid solution (1%, v/v) to prepare the casting solution at the environment. And then, 2 ml TPC solution, 5 wt% in THF solvent, at
concentration ranging from 0.6 to 1.0 mg/ml. 0 C, was slowly added into the beaker drop by drop under a mild
Triethylamine needs to be redistilled to remove the rst and the stirring. The whole beaker was sealed up and kept for 72 h at 0 C.
second amine which will have erce side reaction with the chloride The modied membrane was washed with THF, 1 M NaOH and 1 M
Z. Zhao et al. / Journal of Membrane Science 394395 (2012) 209217 211

HCl subsequently for 3 times, and then double distilled water for ltration data involved in this work with no special descriptions
several times and dried in ambient condition. were all obtained under the same conditions.
Three membrane specimens were tested and the nal results
2.3.4. Chitosan co-modication with GA and TPC were averaged. The commercial UF membrane (Sepro UF, PES10)
First the chitosan was crosslinked with GA to form a bulk was tested for comparison.
crosslinked chitosan, and then the surface of the chitosan was
modied with TPC. The whole process was carried out precisely 3. Result and discussion
in accordance to the separate process mentioned above.
3.1. Electrospinning of PVDF
2.4. Characterization
PVDF nanobers were successfully fabricated in the laboratory.
The viscosity of the chitosan casting solution was measured Fig. 1 showed the morphology of the electrospun PVDF nanobers.
with SNB-1 digital viscosity meter (NiRun Co., Shanghai, China) at The series of SEM photographs demonstrated that with the increase
a constant temperature of 25 C. of the concentration of the PVDF, the diameter of the ber increases;
The morphologies of the electrospun bers and the composited meanwhile, with the increase of the ratio of acetone in the mixed
membranes were observed using scanning electron microscope solvent, the diameter of the ber increase greatly as well. Ignore
(SEM, JEOL JSM-6700F, Japan), at an accelerating voltage of 5 kV. some usual factors in the process, for example, conductivity, elec-
Each sample was sputter-coated with platinum for analysis. tric charge property and surface energy, the dominating factor in
The virgin chitosan and the modied chitosan were tested by this process was that, with the speed-up of the solvent evaporation
FTIR-ATR mode on an infrared spectrometer (IR, BRUKER TEN- rate, the solidication rate of the polymer was speeded up as well,
SOR27, Germany) in the range of 4000600 cm1 . as a result, the diameter of the bers increased. The more uniform
The hydrophilicity performance of the membranes was eval- and thinner the bers are, the higher operating pressure the top
uated on static water contact angle measurement instrument layer could withstand for ltration process. Therefore, the fabrica-
(PowerEach Co., Shanghai, China). tion condition were chosen at the 16 wt% polymer concentration
The water uptake property was determined gravimetrically. The with the ratio of DMF/acetone = 7/3 and the average diameter of
completely neutralized and dried chitosan and GA crosslinked chi- the PVDF nanobers is about 170 nm.
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 3.2. Preparation of three-tier composite membrane
and shaken at 25 C. Every 30 min the lms were removed from
the medium, blotted off the water on the surface and immediately Viscosity of the casting solution was one of the key parameters
weighted. This procedure was repeated until the lms reached con- for the casting process. The thickness of the top layer of CTS ranges
stant weight (equilibrium water uptake). The water uptake (Wu ) of from 200 nm to 800 nm with the change of the concentration of the
the lms was calculated according to the following equation: 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.
Wc W0 Fig. 2 showed the morphology of the three-tier composite mem-
Wu (%) = 100,
W0 branes with a concentration of casting solution of 0.6 wt%. The SEM
where W0 and Wc are the weights of the samples in the dry and images of CTS and modied CTS composite membrane showed little
swollen states, respectively. difference. The smooth top layer surface was kept well after mod-
ication and the thickness of the casting CTS layer was uniform.
2.5. Filtration performance test The thickness of the top barrier layer is one of the most impor-
tant parameter for the nal performance. With the prerequisite of
Bovine serum albumin was separately dissolved in four types enough mechanical strength, the thinner the top layer is the better
of solvent: ultra-pure water and three different buffers, pHs 3, 6, the performance will be.
and 9 (1% acetate acid, phosphate buffered saline and borax salt
dissolved in ultra-pure water). Also these four different solvents 3.3. Modication of CTS with GA and TPC
were prepared as feed solution for ultraltration process. A series
of BSA aqueous solution was detected by ultravioletvisible (UV) The natural polysaccharideschitosan, has a lot of amine groups
spectroscopy at a wavelength of 280 nm. Standard UV absorption which is quite reactive with other groups, for example acyl halides,
curve of BSA was plotted by varying concentrations of the initial aldehyde, peroxide and epoxy. The mechanism of the reactions in
BSA feed solutions, by which the concentration of ltrate solution this work between GA&CTS and TPC&CTS is shown in Figs. 3 and 4.
was determined. The rejection percentage was calculated by using The former is based on Schiff Base Imine Functionality or Michael-
the following equation: type Adducts with Terminal Aldehydes and the latter is based on
Cf Cp electrophilic substitution reaction.
Rejection (%) = 100, Crosslinking chitosan with GA is a general method which has
Cf
been studied by many research groups [41,42]. Fig. 5 showed the
where Cf and Cp represent the BSA concentration of the feed solu- results of FTIR-ATR spectra of the virgin CTS samples, the sam-
tion and that of the ltrate solution, respectively. ples after crosslinking with GA (CTS-GA) and the samples after
The three-tier composite membranes were tested on an ultral- crosslinking with TPC (CTS-TPC). The virgin CTS spectrum showed
tration cup at a constant pressure of 0.2 MPa, an effective ltration the majority of the function groups: the superposition peak of
area of 13.4 cm2 , a constant temperature of 25 C and a stirring rate OH and NH2 band at 34003200 cm1 , C H stretching band at
of 300 rpm. A 10 min pre-compacted process with pure water l- 28702920 cm1 , the bridge oxygen stretching band at 1160 cm1 ,
tration at 0.2 MPa was carried out for each membrane. The BSA and the C O stretching bands at 1070 cm1 and 1030 cm1 . The chi-
concentration of 1 g/L was used, with different types of solvents, tosan used in this work has an average degree of deacetylation of
including pure water, pH 7 buffer, pH 9 buffer and 1%HAc aqueous 80%, so that, the peaks at 1640 cm1 and 1550 cm1 were formed by
solution (pure water as blank test was operated as well). And the 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 213

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 The four types of CTS: virgin CTS, GA crosslinked CTS, TPC mod-
band which is broad and centred near 1585 cm1 . ied CTS and GA, TPC co-modied CTS were subjected to the static
As a result of crosslinking reaction, signicant changes were water contact angle measurement. The results in Fig. 6 showed
observed in the FTIR-ATR spectrum of the crosslinked samples that, even though the amine groups were reacted, the hydroxyl
versus the virgin CTS. The new peak at 1720 cm1 and 1450 cm1 group survived and kept the barrier layer with excellent hydrophilic
indicated the presence of a carbonyl groups and CH2 groups, nature which is very important for anti-fouling property of the
respectively. And at the carbonyl-amide region, because of the ultraltration membranes.
depletion of the NH2 , the corresponding broad band which
is centred near 1585 cm1 , together with the appearance of 3.4. The ltration performance of the composite membranes
the new peak for C N, which can be located anywhere from
1620 cm1 to 1660 cm1 according to the literature [41,42], the Fig. 7 showed the performance of virgin CTS coated compos-
peak at 1640 cm1 was strengthened and meanwhile the peak at ite membranes. Take CTS-1% for example, the low BSA rejection
1550 cm1 was weakened. exposed the low effectiveness of the virgin CTS barrier. Due to
Modication of CTS with TPC is a novel method to modify the the penetration of BSA into the barrier, the water ux became
surface of the CTS ultra-thin barrier. At the alkaline condition, elec- extremely lowered. The thicker the CTS barrier was, the higher
trophilic reagents, acyl chloride was attacked by the nucleophilic BSA rejection and lower water ux were obtained. The inuence
reagent, amino groups, and formed the carbonyl-amide groups. The of the pH condition of the feed solution was also evaluated. Table 2
rise at 1590 cm1 and 1450 cm1 indicated the introduction of the showed the different water ux and BSA rejection of the CTS-1%
benzene ring whose peaks are located at 1600 cm1 ,1580 cm1 , and and CTS-0.6% composite membrane. At pHs 9 and 7, no obvious
1450 cm1 all of which became stronger especially while the ring change was obtained, while at pH 3 (1% acetic acid), at the very
is connected with the C O group due to the conjugation effect. beginning of the ltration test, the water ux became higher and
Also the peak at 870 cm1 of C H band in benzene ring as the cor- the BSA rejection get lower oppositely. After a period of ltration,
roborative evidence could be observed at the ngerprint region. about 45 h, the CTS barrier layer was totally destroyed, and the
The change of the spectrum band from 1700 cm1 to 1500 cm1 BSA solution passed through the membrane directly. The reason is
was inuenced by two simultaneous factors. One was the disap- that, in the acetous condition, the CTS became more swollen; the
pearance of the NH2 , which inuence a broad range centred near potential gaps for water ow through became more possible and
1585 cm1 , to reduce the absorption. While the other one was the thus caused to the poor performance. As time goes on the CTS layer
appearance of aromatic amide, whose peaks located at 1650 cm1 was gradually dissolved, and destroyed at last.
and 1550 cm1 , to raise the absorption. And the former was the For the purpose of obtaining high ux and BSA rejection
dominant factor, so the peaks were weakened. Furthermore, no efciency and also obtaining acid resistance simultaneously, a mod-
peaks were obtained at the range from 1700 cm1 to 1800 cm1 , ied process was carried out.
which indicated that neither ester groups were generated nor resid- First, CTS was crosslinked with GA. The water uptake property of
ual acyl halides retained. 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. Fig. 8. Filtration test of GA crosslinked CTS-0.6% coated NFCMs: R = 0, R = 1/10 and
R = 1/3.
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 reaction completed at a high ratio. The CTS-0.6% was the main
membrane CTS-0.6% has the thinnest barrier layer and the highest choice because it has visibly high ux. The ltration performance
ux for water ltration, so it is the best choice for the modica- of TPC modied CTS coated NFCM was evaluated at the same time.
tion. When the crosslink ratio R 1, the crosslinked CTS barrier After the surface modication, the BSA became more difcult to
layer became too fragile to work, so there is no data for R 1. The pass through the barrier layer, so the high rejection efciency was
results showed that, after the crosslinking, the membranes get a lit- obtained. The results of water ux rate at 71.4 L/m2 h, and BSA
tle increase in rejection efciency of BSA, and decrease in ux rate rejection at 98% (shown in Table 4), was very satisable.
simultaneously. The ltration test showed the consistent results The modication reagent GA was added into the solution of CTS
with the water uptake test. The reason is obviously that, because to form homogeneous solution. With the water solvent evaporat-
of the form of crosslinked network, the CTS barrier layer became ing, both the CTS and GA became concentrated, and at last the CTS
denser and less water swelling. was crosslinked with GA at the bulk level. While the modication
At the ratio R = 1, the crosslinked CTS barrier becomes too fragile regent TPC was added into THF environment with chitosan mem-
to work under pressure, and meanwhile at the ratio R = 1/10, the brane immersed. Chitosan solid surface was wettable with THF and
effect of crosslinking was not enough. So the middle case at the after the reaction between CTS and TPC, the top surface of CTS
ratio R = 1/3 was selected. barrier became denser. The former modication reaction mainly
Second, the CTS barrier was modied by TPC. Long modication occurred in the bulk of chitosan, while the latter occurred at the top
time, about 72 h, was taken to make sure the surface modication 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 4. Conclusion
GA crosslinked CTS coated membranes were immersed into 1%HAc
solution, and subjected to ultrasound treatment for at least 1 h, and The CTS coated, based on nanobrous PVDF scaffold composite
the CTS-GA membrane kept the original morphology well while vir- ultraltration membrane was successfully fabricated and a novel
gin CTS coated membranes was soon totally destroyed. Also the TPC method to modify by GA and TPC was successfully carried out.
modied CTS coated membranes were immersed into 1%HAc solu- With the two steps modication, the top barrier layer of chitosan on
tion, and subjected to the same ultrasound treatment. Relied only the scaffolds of electrospun PVDF nanobers provided an excellent
on the top surface crosslinking, the membranes could not with- performance in the water-protein liquid ltration. The thin-lm
stand the treatment for more than 5 min. composite nanobrous ultraltration membrane gave a result of
The most important advantage for GA crosslinking is the acqui- 70.5 L/m2 h of ux, and 98.9% of BSA rejection, at 0.2 MPa. Compared
sition of acid resistance property for the CTS barrier layer which with the commercial UF membrane (Sepro UF, PES10), 57.1 L/m2 h
makes the membrane to withstand the operation under the acid and 98%, the ltration efciency was enhanced about 25% at a
environment. While the most important advantage for TPC modi- very high rejection efciency level. And the membrane showed a
cation is the increase of surface crosslinking density and greatly very good antifouling property that after 24 h of operation, the ux
increased BSA rejection efciency. So with the combination of the decreased for less than 7%. This work may provide a new direction
two steps of modication, high performance membrane with both for ltration applications.
acid resistance and high BSA rejection efciency was obtained.
The nal performance of the GA and TPC co-modied CTS coated Acknowledgements
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% This work was nancially supported by Main Direction Pro-
BSA rejection, the performance is enhanced for more than 20%. gram of Knowledge Innovation of Chinese Academy of Sciences
Long period performance of the antifouling property is also (KJCX2-YW-H19) and National Natural Science Foundation of China
evaluated. The results were shown in Fig. 9. Take three types of (20904060).
membrane: CTS-1% coated membrane, GA-TPC co-modied CTS-
0.6% coated membrane and the commercial membrane, of which
References
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 [1] J.D. Ferry, Ultralter membranes and ultraltration, Chem. Rev. 18 (1936)
NFCM decrease from 70.5 to 65.6 L/m2 h, while virgin CTS-1% from 373455.
14.8 to 8.32 L/m2 h and commercial UF from 57.1 to 37.8 L/m2 h. [2] 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,
The result revealed that the modied CTS-0.6%-GA-TPC membrane
Nature 452 (2008) 301310.
showed very good antifouling property: after working 24 h, the ux [3] T.A. Tweddle, O. Kutowy, W.L. Thayer, S. Sourirajan, Polysulfone ultraltration
decreased less than 7%. membranes, Ind. Eng. Chem. Prod. Res. Dev. 22 (1983) 320326.
[4] P. Radovanovic, S.W. Thiel, S.T. Hwang, Formation of asymmetric polysulfone
membranes by immersion precipitation. 1. Modeling mass-transport during
gelation, J. Membr. Sci. 65 (1992) 213229.
[5] P. Radovanovic, S.W. Thiel, S.T. Hwang, Formation of asymmetric polysul-
fone membranes by immersion precipitation. 2. The effects of casting solution
and gelation bath compositions on membrane-structure and skin formation, J.
Membr. Sci. 65 (1992) 231246.
[6] I. Pinnau, W.J. Koros, Structures and gas separation properties of asymmetric
polysulfone membranes made by dry, wet, and dry wet phase inversion, J. Appl.
Polym. Sci. 43 (1991) 14911502.
[7] S. Munari, A. Bottino, G. Capannelli, Casting and performance of polyvinylidene
uoride based membranes, J. Membr. Sci. 16 (1983) 181193.
[8] A. Bottino, G. Cameraroda, G. Capannelli, S. Munari, The formation of micro-
porous polyvinylidene diuoride membranes by phase-separation, J. Membr.
Sci. 57 (1991) 120.
[9] D.L. Wang, K. Li, W.K. Teo, Preparation and characterization of polyvinylidene
uoride (PVDF) hollow ber membranes, J. Membr. Sci. 163 (1999) 211220.
[10] Y. Maeda, M. Tsuyumoto, H. Karakane, H. Tsugaya, Separation of waterethanol
mixture by pervaporation through hydrolyzed polyacrylonitrile hollow ber
membranes, Polym. J. 23 (1991) 501511.
[11] I.C. Kim, H.G. Yun, K.H. Lee, Preparation of asymmetric polyacrylonitrile mem-
brane with small pore size by phase inversion and post-treatment process, J.
Membr. Sci. 199 (2002) 7584.
[12] J.J. Qin, F.S. Wong, Y. Li, Y.T. Liu, A high ux ultraltration membrane spun from
PSU/PVP (K90)/DMF/1,2-propanediol, J. Membr. Sci. 211 (2003) 139147.
[13] A. Asatekin, S. Kang, M. Elimelech, A.M. Mayes, Anti-fouling ultraltration
membranes containing polyacrylonitrile-graft-poly (ethylene oxide) comb
copolymer additives, J. Membr. Sci. 298 (2007) 136146.
[14] Y.H. Zhao, B.K. Zhu, L. Kong, Y.Y. Xu, Improving hydrophilicity and protein resis-
tance of poly(vinylidene uoride) membranes by blending with amphiphilic
Fig. 9. The performance of each membrane for long period of operation. hyperbranched-star polymer, Langmuir 23 (2007) 57795786.
Z. Zhao et al. / Journal of Membrane Science 394395 (2012) 209217 217

[15] S.C. Yu, M.H. Liu, Z.H. Lu, Y. Zhou, C.J. Gao, Aromaticcycloaliphatic polyamide [31] D.S. Katti, K.W. Robinson, F.K. Ko, C.T. Laurencin, Bioresorbable nanober-
thin-lm composite membrane with improved chlorine resistance prepared based systems for wound healing and drug delivery: optimization of fabrication
from m-phenylenediamine-4-methyl and cyclohexane-1,3,5-tricarbonyl chlo- parameters, J. Biomed. Mater. Res. B Appl. Biomater. 70B (2004) 286296.
ride, J. Membr. Sci. 344 (2009) 155164. [32] H.F. Jia, G.Y. Zhu, B. Vugrinovich, W. Kataphinan, D.H. Reneker, P. Wang,
[16] D.H. Reneker, I. Chun, Nanometre diameter bres of polymer, produced by Enzyme-carrying polymeric nanobers prepared via electrospinning for use
electrospinning, Nanotechnology 7 (1996) 216223. as unique biocatalysts, Biotechnol. Progr. 18 (2002) 10271032.
[17] J. Doshi, D.H. Reneker, Electrospinning process and applications of electrospun [33] Y.C. Ahn, S.K. Park, G.T. Kim, Y.J. Hwang, C.G. Lee, H.S. Shin, J.K. Lee, Development
bers, J. Electrostat. 35 (1995) 151160. of high efciency nanolters made of nanobers, Curr. Appl. Phys. 6 (2006)
[18] D. Li, Y.N. Xia, Electrospinning of nanobers: reinventing the wheel? Adv. 10301035.
Mater. 16 (2004) 11511170. [34] R.S. Barhate, S. Ramakrishna, Nanobrous ltering media: ltration problems
[19] Z.M. Huang, Y.Z. Zhang, M. Kotaki, S. Ramakrishna, A review on polymer and solutions from tiny materials, J. Membr. Sci. 296 (2007) 18.
nanobers by electrospinning and their applications in nanocomposites, Com- [35] M.G. Hajra, K. Mehta, G.G. Chase, Effects of humidity, temperature, and
pos. Sci. Technol. 63 (2003) 22232253. nanobers on drop coalescence in glass ber media, Sep. Purif. Technol. 30
[20] X.Y. Wang, C. Drew, S.H. Lee, K.J. Senecal, J. Kumar, L.A. Sarnuelson, Electrospun (2003) 7988.
nanobrous membranes for highly sensitive optical sensors, Nano Lett. 2 (2002) [36] R. Gopal, S. Kaur, Z.W. Ma, C. Chan, S. Ramakrishna, T. Matsuura, Electrospun
12731275. nanobrous ltration membrane, J. Membr. Sci. 281 (2006) 581586.
[21] X.Y. Wang, Y.G. Kim, C. Drew, B.C. Ku, J. Kumar, L.A. Samuelson, [37] K. Yoon, K. Kim, X.F. Wang, D.F. Fang, B.S. Hsiao, B. Chu, High ux ultraltra-
Electrostatic assembly of conjugated polymer thin layers on elec- tion membranes based on electrospun nanobrous PAN scaffolds and chitosan
trospun nanobrous membranes for biosensors, Nano Lett. 4 (2004) coating, Polymer 47 (2006) 24342441.
331334. [38] Y. Yoon, B.S. Hsiao, B. Chu, High ux ultraltration nanobrous membranes
[22] D.H. Zhang, Z.Q. Liu, C. Li, T. Tang, X.L. Liu, S. Han, B. Lei, C.W. Zhou, Detection of based on polyacrylonitrile electrospun scaffolds and crosslinked polyvinyl alco-
NO2 down to ppb levels using individual and multiple In2 O3 nanowire devices, hol coating, J. Membr. Sci. 338 (2009) 145152.
Nano Lett. 4 (2004) 19191924. [39] H.Y. Ma, K. Yoon, L.X. Rong, Y.M. Mao, Z.R. Mo, D.F. Fang, Z. Hollander, J.
[23] C. Drew, X.Y. Wang, K. Senecal, H. Schreuder-Gibson, J.N. He, J. Kumar, L.A. Gaiteri, B.S. Hsiao, B. Chu, High-ux thin-lm nanobrous composite ultral-
Samuelson, Electrospun photovoltaic cells, J. Macromol. Sci. Pure Appl. Chem. tration membranes containing cellulose barrier layer, J. Mater. Chem. 20 (2010)
A39 (2002) 10851094. 46924704.
[24] P. Gibson, H. Schreuder-Gibson, D. Rivin, Transport properties of porous mem- [40] K. Yoon, B.S. Hsiao, B. Chu, High ux nanoltration membranes based on inter-
branes based on electrospun nanobers, Colloid Surf. A Physicochem. Eng. facially polymerized polyamide barrier layer on polyacrylonitrile nanobrous
Aspects 187 (2001) 469481. scaffolds, J. Membr. Sci. 326 (2009) 484492.
[25] H. Schreuder-Gibson, P. Gibson, K. Senecal, M. Sennett, J. Walker, W. Yeo- [41] J.D. Schiffman, C.L. Schauer, Cross-linking chitosan nanobers, Biomacro-
mans, D. Ziegler, P.P. Tsai, Protective textile materials based on electrospun molecules 8 (2007) 594601.
nanobers, J. Adv. Mater. 34 (2002) 4455. [42] M.M. Beppu, R.S. Vieira, C.G. Aimoli, C.C. Santana, Crosslinking of chitosan mem-
[26] P.W. Gibson, H.L. Schreuder-Gibson, D. Rivin, Electrospun ber mats: transport branes using glutaraldehyde: effect on ion permeability and water absorption,
properties, AlChE J. 45 (1999) 190195. J. Membr. Sci. 301 (2007) 126130.
[27] G. Verreck, I. Chun, J. Rosenblatt, J. Peeters, A. Van Dijck, J. Mensch, M. Noppe, [43] A. Cooper, N. Bhattarai, F.M. Kievit, M. Rossol, M.Q. Zhang, Electrospinning of
M.E. Brewster, Incorporation of drugs in an amorphous state into electrospun chitosan derivative nanobers with structural stability in an aqueous environ-
nanobers composed of a water-insoluble, nonbiodegradable polymer, J. Con- ment, PCCP 13 (2011) 99699972.
trol. Release 92 (2003) 349360. [44] W. Zhang, G.W. Li, Y.J. Fang, X.P. Wang, Maleic anhydride surface-modication
[28] J.A. Matthews, G.E. Wnek, D.G. Simpson, G.L. Bowlin, Electrospinning of collagen of crosslinked chitosan membrane and its pervaporation performance, J.
nanobers, Biomacromolecules 3 (2002) 232238. Membr. Sci. 295 (2007) 130138.
[29] M.S. Khil, D.I. Cha, H.Y. Kim, I.S. Kim, N. Bhattarai, Electrospun nanobrous [45] J.F. Zheng, A.H. He, J.X. Li, C.C. Han, Polymorphism control of poly(vinylidene
polyurethane membrane as wound dressing, J. Biomed. Mater. Res. B Appl. uoride) through electrospinning, Macromol. Rapid Commun. 28 (2007)
Biomater. 67B (2003) 675679. 21592162.
[30] H. Yoshimoto, Y.M. Shin, H. Terai, J.P. Vacanti, A biodegradable nanober [46] S. Hong, X.H. Zhang, R.Y. Zhang, J. Zhao, C.C. Han, Thickness dependence of
scaffold by electrospinning and its potential for bone tissue engineering, Bio- liquidliquid phase separation in thin lms of a polyolen blend, Macro-
materials 24 (2003) 20772082. molecules 42 (2009) 43494351.