Desalination 343 (2014) 180–186

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

Fouling and rejection behavior of carbon nanotube membranes☆

Seung-Min Park a, Jungwoo Jung a, Sangho Lee a,⁎, Youngbin Baek b, Jeyong Yoon b,
Dong Kyun Seo c, Yong Hyup Kim c
a
Department of Civil And Environment Engineering, Kookmin University Jeongneung-gil 77, Seongbuk-gu, Seoul 136-702, Republic of Korea
b
School of Chemical and Biological Engineering, Seoul National University, Daehak-dong, Gwanak-gu, Seoul 151-742, Republic of Korea
c
School of Mechanical and Aerospace Engineering, Seoul National University, Daehak-dong, Gwanak-gu, Seoul 151-742, Republic of Korea

H I G H L I G H T S

• Vertically aligned carbon nanotube (VA-CNT) membranes were fabricated.

• Fouling and rejection of VA-CNT membrane were compared with those of UF.
• The VA-CNT membranes were modified by graft polymerization method.
• The surface modification improves on performances of VA-CNT membranes.

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

Article history: In recent years, there has been a growing interest in nanostructure membranes made of vertically aligned carbon
Received 3 July 2013 nanotubes (VA-CNT) due to their potential of high water permeability. Nevertheless, membrane fouling is one of
Received in revised form 28 September 2013 the most critical issues in these VA-CNT membranes. Accordingly, this study mainly focused on understanding of
Accepted 3 October 2013
membrane fouling of VA-CNT membranes, which were prepared by thermal chemical vapor deposition (CVD)
Available online 28 October 2013
technique. Surface modification by graft-polymerization of methacrylic acid (MA) was attempted to not only
Keywords:
retard membrane fouling but also improve solute rejection. The resistance-in-series model was applied to
Carbon nanotube characterize the properties of fouling layers. BSA (bovine serum albumin) was used as the model foulant. Results
Vertically aligned carbon nanotube membrane indicated that the VA-CNT membranes had higher fouling propensity than polymeric membranes. After surface
Fouling modification, however, irreversible fouling was significantly reduced in the VA-CNT membranes, which was
Rejection attributed to an increase in hydrophilicity and surface charge. The rejection of BSA by VA-CNT membrane also
Surface modification increased after surface modification, suggesting that the surface charge played an important role in the rejection
of charged molecules.
© 2013 Published by Elsevier B.V.

1. Introduction
Recently, carbon nanotube (CNT) membranes have been investigat-
ed by many researchers as a novel membrane technology for water
treatment [1–3]. When CNTs are used as pores of membranes, they
appear to allow fast fluid flow due to their strong hydrophobicity
[4–6]. Due to its potential, there are a lot of possible applications:
programmable transdermal drug delivery of nicotine [7], biomolecule
separation [8], chemical separation [9], DNA translocation [10], water
desalination [11], natural protein cannel mimicking and gas separation
☆ This is an open-access article distributed under the terms of the Creative Commons
Attribution-NonCommercial-No Derivative Works License, which permits non-commercial
use, distribution, and reproduction in any medium, provided the original author and source
are credited.
⁎ Corresponding author. Tel.: +82 2 910 4529; fax: +82 2 910 8597.
E-mail address: sanghlee@kookmin.ac.kr (S. Lee).
[12]. Nevertheless, relatively few studies have been done in the devel-
opment of CNT membranes for water treatment.
There are several issues in the application of CNT membranes for
water treatment. One of them is fouling of CNT membranes. Since
these membranes are hydrophobic, a rapid membrane fouling is an-
ticipated [13–15]. Another issue is relative low rejection of ions and
small organics by CNT membranes. Multi-wall CNTs generally have
large inner diameters (3 ~ 10 nm), which are not sufficient to reject
ions. Even single-wall CNTs (~ 1 nm) may not be enough to reject
ions [11,16].
Accordingly, this study focused on i) understanding of fouling and
rejection of CNT membranes; and ii) resolving these problems by
surface modification. A theoretical model was applied to analyze the
experimental data. Graft polymerization using methacrylic acid (MA)
was also attempted to reduce fouling and increased rejection. The
performance of the modified membranes was compared with untreated
CNT membrane and commercially-available polymer membranes in
terms of fouling properties and solute rejection.

0011-9164/$ – see front matter © 2013 Published by Elsevier B.V.

http://dx.doi.org/10.1016/j.desal.2013.10.005
 S.-M. Park et al. / Desalination 343 (2014) 180–186 181

Table 1
Summary in characterization of UF and VA-CNT membranes.

Category of membranes Materials Average pore size Density Membrane thickness Wettability Roughness
(nm) (pores/cm2) (μm) (cosΘ) (nm)

UF membrane Polysulfone 6.43 ± 2.49 8.8 × 1010 0.1 ~ 0.4 0.349 5.77 ± 0.24
VA-CNT membrane CNT/epoxy composite 4.87 ± 0.87 6.8 × 1010 200 ± 50 0.012 21.3 ± 5.21

2. Materials & methods
2.1. VA‐CNT membranes & UF membranes
The vertical aligned CNT membrane was made by thermal chemical
vapor deposition (thermal CVD) [17,18]. At 800 °C, Multi-walled CNT
(MWCNT) was grown on substrate Fe/Al2O3/Si at the condition, which
is C2H2 and CH4 gas flowing. After preparation of CNT forests, they
were separated from the substrate and filled by epoxy resin. Epoxy was
chosen as appropriate material to fill the space among CNT due to its
high mechanical strength required for high pressure membrane filtra-
tion. In addition, epoxy is hydrophobic to have high attractive interaction
with CNT. After curing with sufficient time, the CNT-epoxy composites
were cut by microtome (HM 340 E, MICROM Lab., Germany).
Commercially available ultrafiltration membranes (UE4040,
Woongjin Chemical, Korea) were also used for comparison, were kindly
supplied by Woongin Chemical Co Ltd (Korea). The membranes were
made of polysulfone. The membranes were washed several times with
deionized (DI) water and dipped in DI water overnight before use in
order to remove surfactant.
Taiwan). A wettability of both membranes was measured by contact
angle meter (a Krüss DSA 100 goniometer, Krüss GmbH, Germany)
using sessile drop method. Membrane surface roughness was measured
using SPM (scanning probe microscope, XE-100, Park system, USA).
2.2.2. Surface characteristic of membrane
Attenuated total reflection Fourier transform infrared spectroscopy
(ATR-FTIR; Nicolet spectrophotometer 5700, Thermo Electron Corp.,
MA) was used for obtaining chemical and elemental information of mem-
brane surface. In order to analyze the quantitative elemental composition
of membrane surfaces, X-ray photoelectron spectroscopy (XPS) was used.
2.3. Fouling characteristic
2.3.1. Resistances in series model
To analyze the characteristics of membrane fouling, the resistance-
in-series model was applied [19]:
ΔP
Jo ¼ ð1Þ
μ ðRm þ Rir þ Rr Þ

2.2. Membrane characterization where, Jo is a pure water flux, μ is the dynamic viscosity, Rm is the
membrane resistance, ΔP is the trans membrane pressure, Rir is the
2.2.1. Structure of membranes irreversible fouling resistance, and Rr is the reversible fouling resistance.
Table 1 shows fundamental characteristics of membranes, which were
measured by various methods. The CNT/epoxy composites were exam- 2.3.2. Filtration system
ined using field emission scanning electron microscope (FE-SEM, S- The experiments were performed in batch mode using a stirred cell
4700, Hitachi, Japan). The size of the outer and inner diameter of CNTs as shown in Fig. 1. The stirred cell (model 4750, Steriltech™, USA) was
was measured using scanning electron microscopy (HC200-Cu, Electron made of stainless steel. The diameter of the stirred cell was 49 mm
microscopy sciences, USA) and transmission electron microscopy (TEM, and the working volume was 300 ml. The stirred cell was specially
JEM-2100, JEOL, Japan). The average of diameter was analyzed by TEM designed to test small membranes having an effective area less than
images. In addition, microstructure and pores of the VA‐CNT membrane
surface were analyzed by TEM (H7600, Hitachi, Japan), which was pre-
pared by the ultra-microtome (UC6, Leica, Germany).
The VA-CNT membrane thickness was measured using a micrometer.
The effective area of CNT membrane was measured by imaging of CNT
membranes and using area calculation program (Dinocapture, Dino Lite,

Fig. 1. Schematic diagram of dead-end stirred cell filtration system.
Fig. 2. Filtration protocol for accelerated fouling steps: (a) to minimize compaction effects,
DI water was passed through the membrane at the TMP of 1.5 bar for 15 min, (b) initial
water permeability at 1 bar, (c) after the cell was emptied, 20 mg/L BSA was filled and
the 1 bar was re-pressurized, and the filtration was continued until 25 g and 2.5 g of per-
meate were collected, UF and CNT respectively. (d–e) the cell was emptied and refilled
with DI water. And then, washing the membranes at high stirred speed (physically
wash) for 30 min, (f) the water permeability was again measured using DI water.
182 S.-M. Park et al. / Desalination 343 (2014) 180–186
Fig. 3. Size distribution of Ludox® SM and TMA colloidal silica derived from dynamic light
scattering (DLS) analysis. The former particle size is approximately 6.8 nm and the latter is
approximately 18.7 nm.
10 mm2. A magnetic stirrer was positioned just above the membrane.
The working pressure was controlled by a high pressure nitrogen cylin-
der and by a gas pressure regulator. The stirring speed was controlled by
a magnetic stirrer plate. The temperature of the feed solution was ad-
justed to 20 ~ 25 °C and the effect of temperature on viscosity and den-
sity was corrected. Since the experiment was performed in a short
time (normally less than 30min), the variations of the temperature dur-
ing an experiment were smaller than ±1 °C. The permeate flux was
measured using an electronic balance (ARG423, Ohaus, USA) con-
nected to a laptop computer.
A schematic representation of the filtration protocol is shown in
Fig. 2. Each membrane was first compacted for 15 min at 1.5 bar with
Fig. 4. Membrane modification method: (a) Grafting of methacrylic acid to vertically aligned CNT membrane by redox polymerization and (b) schematic diagram of graft polymerization
for surface modification of membrane (UF and VA-CNT).
DI water. Then, the cell was filled with the BSA solution and the cell
was re-pressurized. The operating pressure was 1 bar. After 25 g (UF)
and 2.5 g (CNT) of permeate were collected, the BSA concentration in
the cell and permeated solution were measured. And then, the
membranes were washed by high stirred speed (1200 rpm) for 30 min.
The operating conditions were 1 bar and 1.5 bar pressure and 500
and 1200 rpm stirring speed. These sitting speeds correspond to Re =
0.6 × 105 and 1.4 × 105, respectively. The Reynolds number was based
on the internal radius of the cell and the linear velocity was ωr.
ρωr2
Re ¼ ð2Þ
μ
where ρ is the density, ω is the stirred speed, and r is the radius.
2.3.3. Preparing of solution
The feed solution was prepared using 20 mg/L of BSA in 1 L of 10mM
phosphate buffered saline (PBS) at pH 7.4. The PBS solution consisted of
NaCl (128 mM), KCl (2.7 mM), NaH2PO4 (1.9 mM), and Na2HPO4
(8.1 mM) in DI water [20].
2.4. Rejection characteristic
2.4.1. Materials
To examine the rejection properties of the membranes, BSA, colloidal
silica, dextran, NaCl, and Na2SO4 were used as model solutes. The bovine
serum albumin (BSA, A7906, Sigma Aldrich, USA) was used at 20 mg/L.
The hydrated diameter of BSA is approximately 6 nm (MW: 66 kDa).
The isoelectric point of BSA is 4.7, and it has a charge of about −20.5 elec-
trons at pH=7.4 [21,22]. Protein concentrations were determined by UV/
vis spectrophotometer (DR 4000, Hach, USA) using Bradford assay [23].
The LUDOX® SM (420794, Sigma Aldrich, USA) and LUDOX® TMA
(420859, Sigma Aldrich, USA) colloidal silica were used at 6 mg/L.
Each solution has different particle size. The former particle diameter
is about 6.8 nm and the latter is about 18.7 nm (Fig. 3). The size of
 S.-M. Park et al. / Desalination 343 (2014) 180–186 183

The solute radius may be calculated by the Stokes–Einstein equation:

kT
D¼ ð6Þ
6πηRh

where, k is the Boltzmann constant, T is the absolute temperature, Rh is

the hydraulic radius of the particle, and η is the hydrodynamic boundary
condition.
When membranes have charged surfaces, electrostatic repulsion
may play an important role in rejecting charged solutes. The Donnan
exclusion theory explained the interaction between charging membrane
and solution [16,25]:


 !
RDonnan ¼ 1−
cm
i
ci
¼ 1−
jzi jci
i þ cx
jzi jcm m j j zi
zj
ð7Þ

where ci and cm i are the concentrations of same charge ions in the

solution and in the membrane phase respectively, cm x is the membrane
charge concentration, and subscripts i and j indicate same charge ions
and counter ions.

2.5. Surface modification

2.5.1. Graft polymerization procedure

Fig. 4 summarizes the procedures for the graft polymerization. A 5%
aqueous solution of monomer (methacrylic acid) was prepared with a

Fig. 5. Rejection measured by eight solutions. The lines were the result of a fit using Eq. (4).
(a) Ultrafiltration membrane and (b) VA-CNT membrane.

particle was confirmed by electron light scattering spectrophotometry

(ELS, ELSZ, Otsuka, Japan) using dynamic light scattering (DLS) analysis.

2.4.2. Rejection measurements

Solute rejection (Robs) was calculated from the feed concentration,
cf, and permeate concentration, cP:


cp
Robs ¼ 1− : ð3Þ
cf

Model equations were applied to interpret the results from the

rejection experiments. According to the Spiegler–Kedem equation, the
solute rejection is given by [24]:


σ ð1−F Þ 1−σ
RSK ¼ with F ¼ exp − J ð4Þ
1−σ F P

where, R is calculated rejection, J is a water flux (L/m2 h) P is solute

permeability (L/m2 h), and σ is the reflection coefficient. Here, the
steric hindrance pore (SHP) model can be used to determine σ as a
function of the effective membrane pore radius, rs, and solute radius,
rp. [24]:

! !2 " !2 #
16rs 2 rs rs
σ ¼ 1− 1 þ 1− 2− 1− : ð5Þ
9rp 2 rp rp
Fig. 6. ATR-FTIR spectra for the raw and modified (a) UF membrane, (b) VA-CNT membrane.
184 S.-M. Park et al. / Desalination 343 (2014) 180–186

Table 2 for two membranes were calculated as 6.18 × 1011 cm− 1 and
Relative surface chemical composition of the control and MA modified UF membrane and 9.14 × 1011 cm− 1, respectively.
VA-CNT membrane calculated from XPS scan spectra.
Then, fouling tests were done using the protein (BSA) solution.
Sample Elemental composition (%) Elemental ratio (%) When the BSA solution was filtrate by membranes, the flux was rapidly
C O S C/O declined. The flux of VA-CNT membranes decreased more than 30%
compared with the initial flux. This is attributed to blockage of the
Control UF 78.95 15.59 4.05 19.49
Control CNT 75.96 15.51 6.05 12.55 pores by BSA which can occur due to favorable interactions of the
MA-UF 77.27 17.56 2.9 26.64 hydrophobic surface with BSA. Additionally, it is possible that the
MA-CNT 76.64 19 4.81 4.03 hydrophobic surface of epoxy may accelerate the adsorption of BSA
near the pores. Similar trend has been reported in the literature [29].
After the fouling tests, the resistance-in-series model was applied to
mixture of redox initiators consisting of 40 mg sodium metabisulfite analyze the irreversibility of the fouling. The irreversible resistance, Rir,
(Na2S2O5) and sodium persulfate (Na2S2O8) in the beaker [26–28]. of UF membrane (5.80×1011 cm−1) was lower than VA-CNT membrane
Then, the solution was poured in to the holder containing the raw UF (1.62 × 1012 cm−1). The ratios of irreversible fouling to total resistance
and VA-CNT membranes. After 30 min, the membrane was removed for UF and VA-CNT membranes were 23.7% and 68.8%, respectively.
from holder and washed with DI water. The washed membrane was On the other hand, the ratios of reversible fouling resistance were
stored in DI water for subsequent experiments. 37.6% and 5%, respectively. These results suggest that the fouling of
VA-CNT membrane is irreversible and hard to be recovered.

3. Results & discussion 3.2. Rejection behavior

3.1. Fouling behavior
To begin, the initial water flux tests were conducted using D.I water.
The pure water permeabilities for the VA-CNT membrane and UF mem-
brane were 1000 ±100 L/m2-h-bar (LMH/bar) and 400±10L/m2-h-bar
(LMH/bar), respectively. The intrinsic membrane resistances, RM,
The rejection properties of UF and VA-CNT membranes were com-
pared using various model solutes. Fig. 5 shows the relationship
between solute radius and the rejection. The symbols indicate the
experimentally-determined rejections and the curves indicate the
theoretical rejections calculated using Eq. (5). Using Eq. (7), the solute
radius was calculated as: sodium sulfate 1.1 nm, Ludox® SM 6.8 nm,
BSA 6.9nm, dextran T-40 8.4nm and Ludox® TMA 18.9nm. The average
pore diameter of VA-CNT membrane is 4.87 nm, which was measured
from the TEM images. The size exclusion model based on Spiegler–
Kedem equation reasonably matches the experimental results. Never-
theless, there are deviations between the measured pore radius by
TEM and calculated pore size to match the experimental results. This
could be attributed to the complex rejection mechanisms that may
exist in CNT membranes.
The results in Fig. 5 suggest that the VA-CNT membrane has similar re-
jection to the commercial UF membranes. To use this membrane for desa-
lination, the rejection should be improved. It is possible to increase the
rejection using single wall CNT (SWCNT) which has a diameter of close
to 1 nm. Nevertheless, the use of SWCNT for membrane preparation is
not practical because SWCNT is much more expensive than MWCNT. Un-
fortunately, it is difficult to further reduce the inner diameter using
MWCNT. Therefore, the surface modification was applied to not only to
reduce fouling propensity but also to increase rejection of charged solutes.

Fig. 8. Effect of surface modification in the membrane fouling result in the total resistance,
Fig. 7. Contact angles of the (a) UF membrane and (b) VA-CNT membrane with control Rt, of unmodified CNT membrane and modified decrease from 2.34 × 1012 cm−1 to
and modified membrane by MA. 9.9 × 1011 cm−1, respectively.
 S.-M. Park et al. / Desalination 343 (2014) 180–186
Fig. 9. AFM images of control and modified membrane of VA-CNT membrane: (a) Control-CNT membrane, (b) Control-CNT membrane after BSA filtration, (c) MA-CNT membrane and (d)
MA-CNT membrane after BSA filtration.
3.3. Surface modification
Both VA-CNT and UF membranes were used for surface modification
by the graft polymerization method. After the reaction, ATR-FTIR was
used to verify the formation of carboxylic bonds and the presence of func-
tional group on the membranes. Relative amounts of functional group at-
tachment were compared before and after the surface modification. In
addition, XPS was also used because it is particularly well suited for exam-
ining the skin layer, 1 to 10 nm, of a composite membrane.
Fig. 6 shows the ATR-FTIR results for UF and VA-CNT membranes.
The FTIR data were normalized with 1243 cm−2 (UF) and 1506 cm−2
(VA-CNT). The peaks at 1701 cm−2, which is related to carboxylic
groups, appeared after graft polymerization of MA in both membranes.
The intensity of the peaks increased with increasing the reaction time
Fig. 10. Effect of pH on measured rejection for a 20 mg/L BSA solution.
185
for the polymerization. Moreover, the peaks at 1580 cm−2 and
1450 cm−2, which are associated with the C_C groups, decreased
with the graft polymerization. This result implies that the C_C groups
were changed to C\COOH groups by the radical reaction.
Table 2 shows the elemental composition of the UF and VA-CNT
membranes from XPS measurement. Compared with the control mem-
brane, the modified membranes exhibited a lower percentage of the
284.6 eV peak and higher percentages of the 285.6 eV peak and
288.2 eV peak. These results clearly indicate that the carboxylic groups
were formed on the surface of the modified membranes.
3.4. Effect of surface modification on membrane properties
It was expected that the membrane surface became more hydrophil-
ic as a result of the surface modification. To verify this, the contact angles
were measured before and after the surface modification. As shown in
Fig. 7(a), the contact angle for the control UF membrane was 70°.
After 30 min, 1 h and 2 h of reactions, the contact angles decreased to
52.1°, 49.2° and 39°, respectively. Similar trends were observed for the
VA-CNT membranes in Fig. 7(b). The contact angle for control was
92.1° and decreased to 56.5° after 2 h of reaction. It is evident from
these results that the membrane became more hydrophilic after the
surface modification.
3.5. Effect of surface modification on fouling
To investigate the effect of the graft polymerization on the fouling
propensity of VA-CNT membranes, the resistance-in-series model was
applied after the fouling tests. Fig. 8 compares the hydraulic resistances
for control and modified CNT membranes. The numbers on the bar
graph indicate the absolute value for the resistance. Since the
membrane is more hydrophilic, the intrinsic membrane resistance was
slightly reduced from 6.18 × 1011 cm−1 to 4.63 × 1011 cm−1 after
186 S.-M. Park et al. / Desalination 343 (2014) 180–186
the modification. Moreover, the contribution of irreversible fouling
significantly decreased after the modification (from 1.62 × 1012 cm−1 to
1.39 × 1011 cm−1). As a result, the total resistance for the modified mem-
brane was only 42% of the control CNT membrane. It is likely that the foul-
ing due to BSA adsorption was mitigated making the membrane surface
more hydrophilic or changing the charge of the membrane surface.
Another factor that may affect the fouling is surface roughness. If a
membrane has lower degree of roughness, it will be less susceptible to
foulant deposition. Fig. 9 shows the AFM images for the analysis of
surface roughness. The membrane surfaces before and after fouling
tests were also compared. Before the fouling test, the modified
membrane seems to have smooth surface compared with the control
membrane. After the fouling test, however, the degrees of roughness
seem to be similar. This suggests that the roughness may be related to
the reduction in fouling after the modification.
3.6. Rejection behavior
The rejection of BSA was investigated using the modified CNT mem-
brane, as shown in Fig. 10. The BSA rejection increased from 71% to 90%
as a result of the modification. However, the BSA rejection by the
modified membrane decreased to 72% at the isoelectric point of BSA
(pH 4.7), which is almost identical to the BSA rejection by the control
membrane. It appears that the rejection of BSA is improved by the
surface modification but sensitive to solution pH.
These results are attributed to the rejection mechanisms of the
control and modified CNT membranes. The control CNT membrane,
which does not have strong surface charges, rejects BSA by size exclu-
sion mechanisms. On the other hand, the modified membrane, which
has negative charges by carboxyl groups, rejects BSA by both size exclu-
sion and charge repulsion [25]. The difference between the control
(71%) and the modified membrane (90%) is explained by the charge
repulsion mechanisms. However, at the isoelectric point, the BSA,
which does not have charge, is rejected only by the size exclusion
mechanism. Since there is a much greater change in rejection with pH
for the modified than unmodified membrane, the reduction in fouling
of the modified membrane may be also attributed to charge repulsion.
4. Conclusion
In this study, the VA-CNT membranes, which were prepared by ther-
mal CVD, were investigated and the surface modification technique by
graft-polymerization of MA was applied. The following conclusions
were withdrawn:
(1) The VA-CNT membranes had high water permeability but had
rapid fouling due to hydrophobic interaction between foulants
and the membrane surface was observed. Most fouling of the
VA-CNT membranes was found to be irreversible.
(2) The VA-CNT membranes have similar rejection capability as
commercial polymeric UF membranes. The rejection of nano-
particles larger than 10 nm was very high.
(3) The surface modification by the graft polymerization of MA was
effective to change the characteristics of VA-CNT and UF mem-
branes. The carboxylic groups were introduced and the contact
angle was reduced.
(4) The modified CNT membrane showed lower fouling propensity
than the control CNT membrane. The irreversible fouling was
substantially decreased by the modification.
(5) The BSA rejection is increased by the modification, which is
probably because of the charge repulsion mechanism.
Acknowledgments
This research was supported by the K-water Research & Business
Project (K_RBP-1) through the K-water research center grant funded
by Korea Water Resources Corporation (K-water).
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