Journal of Membrane Science 455 (2014) 15–23

Contents lists available at ScienceDirect

Journal of Membrane Science

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

Surface fluorination of polyamide nanofiltration membrane

for enhanced antifouling property
Yafei Li a, Yanlei Su a,b, Xueting Zhao a, Runnan Zhang a, Jiaojiao Zhao a, Xiaochen Fan a,
Zhongyi Jiang a,b,n
a
Key Laboratory for Green Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
b
Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China

art ic l e i nf o a b s t r a c t

Article history: A new kind of fluorinated polyamine was successfully synthesized and grafted onto the polyamide
Received 21 August 2013 membrane surface to fabricate an antifouling nanofiltration membrane with low surface free energy.
Received in revised form The surface composition of the fluorinated polyamide nanofiltration membrane was confirmed
15 November 2013
by Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The
Accepted 24 December 2013
Available online 2 January 2014
membrane cross-section morphology was observed by a field emission scanning electron microscopy
(FESEM). The presence of perfluoroalkyl groups on the membrane surface significantly lowered the surface
Keywords: free energy from 60.0 to 44.4 mJ/m2. The filtration experiment results indicated that the surface fluorination
Fluorinated polyamine did not lower the separation performance of the polyamide nanofiltration membrane significantly. The
Surface grafting
antifouling experiment results demonstrated that the fluorinated polyamide nanofiltration membranes
Polyamide nanofiltration membrane
exhibited superior antifouling property, that is, high flux recovery ratio (
98.5%) and low total flux decline
Low surface free energy
Antifouling ratio (
11%) during protein aqueous solution and humic acid aqueous solution filtration.
& 2013 Elsevier B.V. All rights reserved.

1. Introduction
Membrane fouling is a major hindrance to the effective appli-
cation of nanofiltration (NF) technology in water treatment,
pharmaceuticals, and biochemical industries [1–8]. Fouling leads
to a decrease in membrane performance, which, in turn, increases
the overall energy requirement of the separation process and
decreases membrane life [9]. Thus, fouling control is one of
the most pressing challenges faced by the membrane science
community. Pretreatment of feed solution and/or chemical clean-
ing are popular approaches to cope with membrane fouling [10].
However, these approaches would dramatically increase the
operation and maintenance costs of the membrane process.
Therefore, there is significant interest in enhancing membrane
fouling resistance and fouling release property to reduce the
burden of feed pretreatment and lower the cleaning cost.
Most state-of-the-art nanofiltration membranes are currently
the thin-film composite (TFC) membranes, comprising a thin
selective active layer on a porous support. As the benchmark
material for the active layer, polyamide shows unrivaled perme-
ability and selectivity performance and a high degree of tenability
n
Corresponding author at: Key Laboratory for Green Technology of Ministry of
Education, School of Chemical Engineering and Technology, Tianjin University,
Tianjin 300072, China. Tel.: þ 86 22 27406646; fax: þ 86 22 23500086.
E-mail address: zhyjiang@tju.edu.cn (Z. Jiang).
in the membrane process [11]. The active layer surface properties
including hydrophilicity, roughness and charge are reported to
influence fouling [12]. For better antifouling performance, efforts
toward membrane active layer modification have focused on
rendering the surface more hydrophilic, smooth, and less charged
[13]. Examples include the production of novel polyamide-based
materials with tailored chemistry and morphology achieved by the
addition of monomers or variation of conditions during interfacial
polymerization [14–16]. However, the unsurpassed separation
properties of polyamide limit the range of improvements that
can be made following this pathway. Other studies have investi-
gated modifications of the thin film surface by postfabrication
procedures [12,17]. So far, majority efforts are devoted to enhan-
cing the fouling resistant property of the membrane, that is to say,
effectively preventing foulants from arriving at membrane surface
via the nonspecific adsorption. Probably, weakening the interfacial
interaction between membrane and foulants, so that attached
foulants are more easily removed, may be another strategy to
tailor membrane antifouling characteristics.
The surface free energy of a solid surface gives a direct
indication of intermolecular or interfacial attractive forces [18].
A number of studies demonstrated that bacterial and organism are
less prone to adhere or attach to low energy surfaces and easier to
clean because of weaker binding force [19,20]. Silicone elastomers
and fluoropolymers, as the two major polymeric materials with
low free energy, have been wildly used in many antifouling fields

0376-7388/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.memsci.2013.12.060
16 Y. Li et al. / Journal of Membrane Science 455 (2014) 15–23
including marine coatings and membrane separation fields. Foul-
ing release coatings as toxin-free alternatives have gained many
attention after the prohibition of tributyitin (TBT) contamination
by the International Maritime Organization (IMO) [21]. Currently,
several surface active block copolymers with fluoroalkyl side
chains [22,23], semifluorinated block copolymers [24,25] and
perfluoropolyether/poly(ethylene glycol) networks [26,27] have
been explored as fouling release coatings. Ober and coworkers
have also developed amphiphilic coatings with silicone segments
as fouling release moieties and heightened their importance in
reducing potential environmental impact [28–30]. Recently,
fluorine-containing copolymers and silicone-containing copoly-
mers are also used as additives in non-solvent-induced phase
separation (NIPS) process to fabricate the ultrafiltration (UF)
membrane, and the membrane displayed the excellent ability to
resist and release various foulants [31–34]. Grafting perfluoroalkyl
groups onto UF membrane surface has also been reported to
improve the fouling release property of the membrane [35].
However, to the best of knowledge, no report has been found for
improving the antifouling property of nanofiltration membranes
by minimizing the interaction forces between nanofiltration
membrane and foulants via low surface free energy strategy.
In this study, to prepare an antifouling NF membrane with low
surface free energy, a new kind of fluorinated polyamine was
synthesized by perfluorooctanoic acid (PFOA) and triethylenete-
tramine (TETA) via condensation reaction. The fluorinated poly-
amine was then grafted onto polyamide NF membrane surface
through the acylation reaction between the amine groups of
fluorinated polyamine and the carbonyl groups on polyamide NF
membrane. The membranes were characterized by contact angle,
surface free energy, SEM, FTIR and XPS. The permeation and
rejection properties, the antifouling behavior of fluorinated poly-
amide NF membrane in filtration of protein and humic acid were
explored.
2. Experimental section
2.1. Materials
Polyethersulfone (PES, 6020 P) was purchased from BASF Co.
(Germany) and dried at 110 1C for 12 h before use. Poly (ethylene
glycol) (PEG, Mw ¼2000), N, N-dimethylformamide (DMF), n-hep-
tane, xylene, ethanol, Na2SO4, MgSO4 and MgCl2 were purchased
Fig. 1. Schematic diagram of fabricating polyamide NF membrane (TFC membrane) and grafting fluorinated polyamine onto the surface of polyamide NF membrane.
from Kewei Chemical Reagent Co. (Tianjin, China). Trimesoyl
chloride (TMC) was purchased from Alfa Co. (USA). Piperazidine
(PIP), triethylenetetramine (TETA) and humic acid (HA) were
received from Guangfu Fine Chemical Research Institute (Tianjin,
China). Perfluorooctanoic acid (PFOA) was purchased from Boman
Chemical CO. LTD. (Zhangjiagang, China). Bovine serum albumin
(BSA) was purchased from Institute of Hematology, Chinese
Academy of Medical Science (Tianjin, China). Orange GII was
purchased from Dingguo Bio-Technology Co. (Beijing, China). The
water used was deionized water at pH 6.0.
2.2. Synthesis of a new kind of fluorinated polyamine
Fluorinated polyamine was synthesized by condensation reac-
tion in the xylene solutions. PFOA (4.64 g, 10 mmol), xylene
(50 mL) and TETA (1.61 g, 11 mmol) were put into a three-necked
round bottom flask provided with a reflux condenser and a
mechanical stirrer. The reaction flask was placed in an oil bath
and the mixture was refluxed with rapid mechanical stirring at
130 1C for 4 h. After reacting for 4 h, the obtained polyamine
solution was then placed on the rotary evaporator to remove
solvent and by-product water. The fluorinated polyamine was then
oven-dried to a constant weight.
To confirm the successful synthesis of the fluorinated poly-
amine, the product was analyzed by Fourier transform infrared
spectroscopy (FT-IR). The sample was dissolved in ethanol and
sprayed on a KBr plate. Transmittance spectra were obtained in the
region of 4000–400 cm  1 with resolution 4 cm  1 for 64 scans.
2.3. Preparation and surface fluorination of the polyamide NF
membrane
PES ultrafiltration membranes were used as the porous sup-
port. The detailed fabrication process had been described in our
previous works [36]. The PES support was first wetted in PIP
aqueous solution with PIP concentration of 0.30 wt%. After 30 min,
the residual water on the surface was drained off using filter
papers. Second, the PIP-saturated support membrane was
immersed for 120 s in a 0.15 wt% TMC in n-hexane to form the
ultrathin polyamide layer by interfacial polymerization. Third, the
membrane was taken from organic phase and air dried at room
temperature for 30 min to allow the n-heptane to evaporate and
subsequently post-treated for attaining the desired stability of the
formed structure.
 Y. Li et al. / Journal of Membrane Science 455 (2014) 15–23
The polyamide NF membrane was then immersed in the
fluorinated polyamine aqueous solution with the fluorinated
polyamine concentration of 0.5, 1.0, 1.5 wt%, respectively. The
acylation reaction of fluorinated polyamine and the carboxyl group
on polyamide NF membrane at three different temperatures
(40 1C, 60 1C, 80 1C) for 3 h were used to graft perfluoroalkyl group
onto the polyamide NF membrane surface. Then the fluorinated
polyamide NF membrane was taken out, rinsed entirely with
ethanol (50%) and deionized water, and stored in deionized water.
The schematic diagram of preparation and surface fluorination of
polyamide NF membrane was described in Fig. 1. The fluorinated
polyamide NF membranes were designated as Fm-PA-n, where the
m indicated the fluorinated polyamine concentration of m wt% and
the n indicated the reaction temperature of n 1C.
2.4. Characterization of the fluorinated polyamide NF membrane
The polyamide NF membrane and the fluorinated polyamide
NF membrane used for chemical structure and morphology
characterization of the skin layer were freeze-drying for 12 h.
The cross-section (broken in liquid nitrogen) morphologies of the
membranes were observed by a field emission scanning electron
micro-scope (FESEM, Nanosem 430) measurement. The membrane
samples were sputtered gold prior to SEM analysis.
Fourier transform infrared spectroscopy (Bruker Vertex 80 V)
was used to investigate the surface chemical structure of the
membranes. Transmittance spectra were obtained in the region of
4000–400 cm  1 with resolution 4 cm  1 for 64 scans. The experi-
ments ran with air as the background and all the spectra were
baseline corrected.
The surface compositions of the membranes were character-
ized by X-ray photoelectron spectroscopy (XPS). XPS measure-
ments were performed on a Kratos Axis Ultra DLD (delay line
detector) spectrometer equipped with a monochromatic Al–Ka X-
ray source (1486.6 eV). All XPS spectra were recorded using an
aperture slot of 300  700 μm, survey spectra were collected over a
range of 0–1100 eV, and the takeoff angle of the photoelectron was
set at 901.
The static contact angle measurements were conducted on the
membrane surfaces by a contact angle goniometer (JC2000C
Contact Angle Meter, Powereach Co., Shanghai, China) at tempera-
ture 257 0.5 1C. At least five contact angles at different locations
on one surface were averaged to get a reliable value.
The surface free energy (γ) was calculated using three-liquid
Lifshitz–van der Waals acid–base model with following equations
[37]:
qffiffiffiffiffiffiffiffiffiffiffiffiffi
γ i ¼ γ LW þ 2 γ iþ γ i
i was filtered through the membranes for 24 h and foulant solution
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffiffi
s γL þ
γ L ð1 þ cos θÞ ¼ 2ð γ LW LW γ sþ γ L þ γ s γ Lþ Þ
where θ was the Young contact angle, i denoted either a solid
þ
(S) or a liquid (L) phase and γ LW
i , γi and γ i (mJ/m2) were the
Lifshitz–van der Waals, acid and base components, respectively.
Two polar liquids (water and glycerol) and one apolar liquid
(diiodomethane) were selected as test liquids.
The zeta potential was measured using a SurPASS Electrokinetic
Analyzer (Anton Paar KG, Austria) equipped with a plated sample
cell. The measurements were carried out at temperature
25 70.5 1C in KCl solution (0.001 M, pH 6.0). Prior to use, the
samples were conditioned in 0.001 M KCl solution for at least 24 h.
The resultant Zeta potential was calculated using the Helmholtz–
Smoluchowski equation.
17
2.5. Separation property of the fluorinated polyamide NF membrane
The performance evaluation was carried out with a dead end
filtration system. The system consisted of a filtration cell with a
volume capacity of 200 mL (effective membrane area was
28.7 cm2, Model 8200, Millipore Co., USA) and a storage tank with
volume of 1.0 L. The operation pressure in the system was main-
tained by nitrogen gas. All the NF experiments were carried out
under the constant pressure of 0.20 MPa, temperature of 257 1 1C
and a stirring speed of 400 rpm. Prior to the filtration experiments,
each membrane was first immersed in deionized water and then
precompacted under 0.25 MPa for 0.5 h using deionized water. The
water flux (Jw1) was measured at 0.2 MPa and calculated by the
following equation:
V
J w1 ¼ ð3Þ
AΔt
where V (L) was the volume of permeated water, A (m2) was the
membrane area and Δt (h) was the permeation time.
To determine the rejection property of the polyamide NF
membrane and the fluorinated polyamide NF membrane, the filter
cell was filled with aqueous solutions of Orange GII or inorganic
salts. The concentration of Orange GII and inorganic salts in feed
solutions was approximately 0.1 g/L and 1.0 g/L. The rejection ratio
(R) was defined as
 
Cp
R ¼ 1  100% ð4Þ
Cf
where Cp and Cf were the solute concentration of permeate and
feed solution, respectively. Salt concentrations of aqueous MgCl2,
MgSO4 and Na2SO4 solutions were measured by electrical con-
ductivity (DDS-11A, Shanghai Leichi Instrument Co., Shanghai,
China). Orange GII concentration was determined with a UV–vis
spectrophotometer (Hitachi UV-2800, Hitachi Co., Japan) at a
wavelength of 485 nm.
2.6. Antifouling property of the fluorinated polyamide NF membrane
In the antifouling property evaluation experiments, BSA and HA
were used as representative pollutants of protein and natural
organic matter (NOM) in natural water source, respectively. The
foulant concentrations in feed solutions were 1.0 g/L. The anti-
fouling experiment was carried out as follows: Each membrane
was initially pressurized under 0.25 MPa for stable water flux
before test (usually 30 min) and the pure water flux, Jw1 was
measured at a transmembrane pressure of 0.2 MPa for 4 h. Then
the stirred cell and solution reservoir were filled with foulant
solution and deionized water, respectively. The foulant solution
ð1Þ
flux after 24 h of filtration, Jp and pure water flux of these
membranes after 30 min of water washing, Jw2 was also measured.
ð2Þ Several indexes including flux recovery ratio (FRR), total flux
decline ratio (DRt), reversible flux decline ratio (DRr) and irrever-
sible flux decline ratio (DRir) were used to analyze the antifouling
property in details [32]. Those ratios were defined and calculated
as follows:
 
J
FRR ¼ w2  100% ð5Þ
J w1
 
J w1  J p
DRt ¼  100% ð6Þ
J w1
 
J w2  J p
DRr ¼  100% ð7Þ
J w1
18 Y. Li et al. / Journal of Membrane Science 455 (2014) 15–23
 
J 3.2. Characterization of the fluorinated polyamide NF membrane
DRir ¼ 1  w2  100%
J w1
The lower DRt and higher FRR values meant the better anti-
fouling property of the membrane in separation process.
3. Results and discussion
3.1. Characterization of the fluorinated polyamine
Perfluoroalkyl materials have been widely used to yield sur-
faces with low surface free energy, which will endow surfaces
with low-adhesive property towards oil, biological foulants and
other unwanted contaminants. To construct an antifouling fluori-
nated NF membrane surface with low surface free energy, a new
kind of fluorinated polyamine was synthesized by the condensa-
tion of PFOA and TETA. Synthesis route for the fluorinated
polyamine was as follows:
CF3 ðCF2 Þ6 COOH þ NH2 ðCH2 CH2 NHÞ3 H-C7 F15 COOH
 NH2 ðCH2 CH2 NHÞ3 H
 H2O
C7 F15 COOH  NH2 ðCH2 CH2 NHÞ3 H - C7 F15 CONHðCH2 CH2 NHÞ3 H
Δ group. Both of those peaks verified the polyamide covered on the
When mixing TETA with PFOA, an acid–base reaction occurs
first to obtain an ammonium salt. Then direct condensation of the
salt can be achieved at high temperature to form an amide bond.
The synthesized fluorinated polyamine was pale yellow viscous
substance, in a yield of 80.4%.
Fig. 2 showed the FT-IR spectra and the chemical structure of
the fluorinated polyamine. The peaks at 1553 cm  1 and
1692 cm  1 observed in the spectrum were assigned to the bend-
ing vibration band of the amine N–H groups and the stretching
vibration band of the amide CQO groups, respectively. The peaks
at 2952 cm  1 and 1465 cm  1 were taken as the asymmetric
stretching vibration band and asymmetric bending band of
methylene. Meanwhile, the broad adsorption band at 3281 cm  1
could be assigned to N–H stretching vibration, which proved that
the surplus amino existed after condensation reaction. Addition-
ally, the peaks at 1207 cm  1 and 1148 cm  1 observed in the
spectrum were relevant to the CFx stretching mode. Those absorp-
tion peaks of a stretching vibration at 1692 cm  1 (amide I, CQO
stretching vibrations of amide) and 1553 cm  1 (amide II, in-plane
N-H bending) confirmed the successful synthesis of the fluori-
nated polyamine.
Fig. 2. FTIR spectra of the synthetic fluorinated polyamine (Inset: Chemical
structure of the fluorinated polyamine).
ð8Þ
Since the interfacial polymerization concept was put forward by
Morgan and Kwolek [38], it has been developed as a dominating
method for preparing polyamide NF membranes. The interfacial
polymerization reaction is self-inhibiting through passage of a
limited supply of reactants to the already formed layer, resulting in
an extremely dense thin film on the top of porous support. The cross-
section morphology of composite membranes was visualized by
FESEM. Fig. 3(a) showed the overall view of the polyamide NF
membrane, which was composed of a thin polyamide active layer
and porous PES support. High resolution image (b) showed the
morphology of upper surface. No significant change of overall
morphology between the polyamide (PA) NF membrane and the
fluorinated polyamide NF membranes (F1.0-PA-60) (in Fig. 3(c) and
(d)) could be observed, which indicated that the grafting would not
alter the bulk structure of the polyamide NF membrane considerably.
FT-IR spectra were used to analyze the changes in chemical
composition of polyamide NF membrane and the fluorinated
polyamide NF membrane. Fig. 4 showed the FT-IR spectra of PES
substrate, polyamide NF membrane and the fluorinated polyamide
NF membrane (F1.0-PA-60). Beside the typical PES bands of the
substrate, the spectrum of polyamide NF membrane exhibited the
absorption peaks at 1624 cm  1 and 1441 cm  1, which were
assigned to the stretching vibration band of the amide CQO
PES substrate was formed during the interfacial polymerization
reaction. Additionally, the peak at 1360 cm  1 observed in the
spectrum of the F1.0-PA-60 membrane was relevant to the CFx
stretching mode. This peak confirmed the fluorinated polyamine
had been anchored on the polyamide NF membrane surface.
The chemical feature in the near-surface region of PES substrate,
the polyamide NF membrane and the fluorinated polyamide NF
membrane was further determined by XPS. In Fig. 5(a), XPS spectra
of the polyamide NF membrane revealed the main contents on the
surfaces were carbon (C), nitrogen (N) and oxygen (O) elements.
Sulfur (S) is one element of PES substrate (the atom percent, 2.5%);
however, the sign of S element did not appear on the XPS spectra of
the polyamide NF membrane, which clearly demonstrated that there
were dense polyamide thin films due to interfacial polymerization
upon the PES substrate. Four characteristic XPS signals for C, N, O and
fluorine (F) were clearly observed in the fluorinated polyamide NF
membrane (F1.0-PA-60). The F 1s peak at 687.0 eV appeared on the
fluorinated polyamide NF membrane demonstrated that the fluori-
nated polyamine was successfully grafted onto the membrane sur-
face. The C 1s core level XPS spectra of the fluorinated polyamide NF
membrane was showed in Fig. 5(b), which could be further fitted
with five peaks using a sum of Lorentzian–Gaussian functions. The C
1s component peaks at the binding energy of 284.6, 285.7, 287.3, 291
and 293.2 eV were attributed to C–C, C–N, CQO, CF2 and CF3,
respectively. The N 1s core-level XPS spectra of the fluorinated
polyamide NF membrane could be resolved into two peaks at the
binding energy of 398.3 and 399.2 eV for the N–C and N–H groups,
respectively. The fluorinated polyamine was the only source of CF2,
CF3 and N–H, which indicated that the fluorinated polyamine had
been successfully grafted onto the polyamide NF membrane surface.
Table 1 presented the static water contact angle of the polyamide
NF membrane and the fluorinated polyamide NF membranes. After
grafting fluorinated polyamine onto the polyamide NF membrane
surface, the contact angles remarkably increased from 30.070.51 of
polyamide NF membrane to 68.872.21 of F1.5-PA-60 membrane. This
result was in agreement with the surface elemental analysis by XPS.
Introducing fluorocarbon groups onto the membrane surface
will endow a low surface free energy property of membrane and
show a decrease in hydrophilicity of membrane. Table 1 also summar-
ized the obvious decrease of γ, along with γd and γp, for the fluorinated
 Y. Li et al. / Journal of Membrane Science 455 (2014) 15–23
Fig. 3. Cross-section morphologies of (a) polyamide NF membrane (PA) and (c) fluorinated polyamide NF membrane (F1.0-PA-60). (b) and (d) were the high resolution
images of upper surface for (a) and (c).
Fig. 4. FT-IR spectra of PES substrate, polyamide NF membrane (PA) and fluorinated
polyamide NF membrane (F1.0-PA-60).
polyamide NF membrane compared with the pristine polyamide NF
membrane. The surface free energy (γ) decreased from 60.0 mJ/m2 of
polyamide NF membrane to 44.4 mJ/m2 of F1.5-PA-60 membrane. The
surface free energy of a solid surface is an index of intermolecular or
interfacial attractive forces. These low surface free energy properties of
the fluorinated polyamide NF membrane would be expected to
minimize the adhesion propensity and facilitate the detachment of
foulants from membrane surface [39,40].
19
Streaming potential measurement was conducted to explore the
surface charge properties of the composite membranes. Zeta potential
versus concentration of fluorinated polyamine and reaction tempera-
ture data were shown in Fig. 6. Fig. 6(a) showed that the zeta potential
decreased from 45.970.9 mv to 41.970.4 mv,  41.370.2 mv
and  38.270.3 mv with the fluorinated polyamine concentration
increasing from 0 (unmodified membrane) to 0.5%, 1.0%, 1.5%. Fig. 6
(b) showed that the zeta potential decreased from  45.970.9 mv
to  42.370.5 mv,  41.370.2 mv and  40.570.5 mv with the
reaction temperature increasing from 0 (unmodified membrane) to
40 1C, 60 1C, 80 1C. For all the NF membranes in this study, the surface
charge was negative at pH 6, which was attributed to the carboxyl
groups dissociated from unreacted acid chlorides of TMC. The existed
carboxylic acid on the composite membrane would be further reacted
with amine and then lowered the surface charge. As we know, the
degree of acylation reaction between carboxylic acid and amine
increases with the increase of the fluorinated polyamine content and
reaction temperature. Therefore, zeta potential would increase with
the increase of the fluorinated polyamine content and reaction
temperature.
3.3. Separation performance of the fluorinated polyamide NF
membrane
Flux and rejection were two important parameters in the
design, application and economic feasibility analysis for the NF
process. In this study, the influence of the fluorinated polyamine
20 Y. Li et al. / Journal of Membrane Science 455 (2014) 15–23

F1S Atomic% 25000

O1S C1S C 50.75
N1S
O 13.6
20000
N 9.14
F 26.51
F1.0-PA-60 15000
Atomic%
C 72.07

C/S
C-C
O 15.99 10000 -CO
-CF
N 11.93 2
PA C-N
Atomic% -CF
3
5000
C 70.4

S2p
S2s
O 27.1
PES 0
S 2.5

800 600 400 200 0 300 295 290 285 280

Binding Energy (eV) Binding Energy (eV)

8000

6000
C/S

4000
CN

2000 NH

0
404 402 400 398 396 394
Binding Energy (eV)

Fig. 5. (a) XPS spectra of PES substrate, the polyamide NF membrane (PA) and fluorinated polyamide NF membrane (F1.0-PA-60) surfaces; (b) C1s core level spectra resolving
results of F1.0-PA-60 membrane; (c) N1s core level spectra resolving results of F1.0-PA-60 membrane.

Table 1
Water contact angles and surface free energy parameters of the polyamide NF membrane (PA) and the fluorinated polyamide NF membranes (F-PA).

Membrane Surface reaction Content of fluorinated Contact angle (deg) Surface free energy (mJ/m2)
temperature (1C ) polyamine (wt%)
Water γ γp γd

PA – – 30.0 60.0 13.9 46.1

F0.5-PA-60 60 0.5 57.7 51.0 10.9 40.1
F1.0-PA-60 60 1.0 62.7 46.1 9.1 37.0
F1.5-PA-60 60 1.5 68.8 44.4 7.9 36.5

concentration and the reaction temperature on membrane perfor-
mance was investigated to obtain an optimal condition. The fluxes
of all the membranes were about 15.0 72.0 L/m2 h, which indi-
cated that grafting fluorinated polyamine onto polyamide NF
membrane surface did not affect the permeation flux too much.
Fig. 7 presented the effect of fluorinated polyamine concentration
on the membrane rejection performance. The experimental results
demonstrated that increasing the content of fluorinated polyamine
would reduce the rejection ratio of salts. For example, the rejection
ratio of Na2SO4 decreased from 87.6% of polyamide NF membrane
to 66.1% of F1.5-PA-60 membrane. Fig. 8 presented the effect of
temperature of acylation reaction on the fluorinated NF membrane
separation performance. The experimental results showed that the
higher reaction temperature led to a lower rejection. The rejection
ratio of Na2SO4 decreased from 87.6% of polyamide NF membrane
to 79.5% of F1.0-PA-80 membrane. The lower rejection ratio was
attributed to the fewer negative charge of membrane after surface
acylation reaction. According to the electrostatic repulsive inter-
action mechanism, the less negative charge membrane surface
(the higher zeta potential) will result in a lower rejection to salt
with high-valent anion, which was consistent with the zeta
potential in this study. Since the degree of acylation reaction
increases with the increase of fluorinated polyamine content
and reaction temperature, the rejection to inorganic salts would
decrease accordingly. However, it should be mentioned that the
rejection ratio of Orange GII was all above 90.0%, which indicated
surface grafting did not considerably lower the rejection perfor-
mance of polyamide NF membrane.
 Y. Li et al. / Journal of Membrane Science 455 (2014) 15–23 21

Fig. 8. Effect of reaction temperature on the rejection behavior. (*0 1C represents

the unmodified polyamide NF membrane.).

1.0

Normalized flux
0.8

Water Feed solution Water

0.6 F1.0-PA-60 with 1g/L BSA

F1.0-PA-60 with 1g/L HA
PA with 1g/L BSA
PA with 1g/L HA
0.4
0 5 10 15 20 25 30
Operation time (h)
Fig. 6. Effect of fluorinated polyamine concentration (a) and reaction temperature Fig. 9. Time-dependent normalized flux for the polyamide NF membrane (PA) and
(b) on the Zeta potentials. the fluorinated polyamide NF membrane (F1.0-PA-60) membrane during BSA and
HA solution NF measurement.

100

Table 2
80 Antifouling indexes (DRt, DRr, DRir and FRR) of the polyamide NF membrane (PA)
and fluorinated polyamide NF membrane (F1.0-PA-60) during BSA and HA solution
Rejection (%)

nanofiltration measurement.
60
MgSO4
Antifouling indexes (%) BSA HA
40 Na2SO4
MgCl2 PA F1.0-PA-60 PA F1.0-PA-60

20 Orange GII DRt 25.9 8.0 22.5 11.8

DRr 17.8 6.3 12.0 10.3
DRir 8.1 1.7 10.5 1.5
0
0 0.5 1 1.5 FRR 91.9 98.3 89.5 98.5

Content of FPA (wt.%)

Fig. 7. Effect of fluorinated polyamine concentration on the rejection behavior. (*0
represents the unmodified polyamide NF membrane.).
3.4. Antifouling property of the fluorinated polyamide NF membrane
Antifouling property was very important for the practical
application of nanofiltration membranes [41]. BSA and HA were
chosen as model protein and natural organic matter (NOM) in
water to evaluate the antifouling property of the polyamide NF
membrane and the fluorinated polyamide NF membranes in dead-
end mode. The molecular sizes of those foulants were larger than
the pore size of nanofiltration membranes, which did not pene-
trate into the pores and only cause surface fouling. In Fig. 9, the
flux declined notably within the first 8 h, which were caused by
concentration polarization and membrane fouling. In the sequen-
tial operation, the deposition and re-suspension of foulants (BSA
or HA) reached equilibrium due to the rigorous stirring near the
membrane surface, so that a stable flux was obtained. Finally, the
flux recovered to a stable high-level after simple water washing.
And flux recovery ratio was recorded to evaluate the antifouling
property of the membrane.
The flux decline ratio and flux recovery ratio of the polyamide
NF membrane and the fluorinated polyamide NF membrane were
presented in Table 2. The polyamide NF membrane exhibited
relatively high flux decline, with DRt as high as 25.9% in filtration
of BSA solution. After fluorination treatment, the decrease of DRt,
DRir and DRr values and the increase of FRR values were observed.
The fluorinated polyamide NF membrane (F1.0-PA-60) exhibited
only 8.0% total flux decline and about 98.3% permeation flux
recovery, and almost no irreversible flux decline occurred.
In filtration of HA solution, the polyamide NF membrane exhibited
22.5% total flux decline compared with 11.8% total flux decline
of the fluorinated polyamide NF membrane (F1.0-PA-60). After
30 min hydraulic washing, the FRR values were 89.5% and 98.5%
22 Y. Li et al. / Journal of Membrane Science 455 (2014) 15–23

for the polyamide NF membrane and the fluorinated polyamide NF R rejection ratio (%)
membrane, respectively. Cp solute concentration of permeate solution
Foulants can adsorb to the membrane surface due to hydro- Cf solute concentration of feed solution
phobic interactions, hydrogen bonding, van der Waals attractions, FRR flux recovery ratio (%)
and electrostatic interactions [42]. Therefore, an effective method to DRt total flux decline ratio (%)
reduce membrane fouling is to lower these adsorptive interactions DRr reversible flux decline ratio (%)
and enhance repulsive interactions between foulants and mem- DRir irreversible flux decline ratio (%)
branes [43,44]. In this study, grafting the fluorinated polyamine γ surface free energy (mJ/m2)
onto the polyamide NF membranes could effectively lower the γp polar components of surface free energy (mJ/m2)
surface free energy of these membranes, which would reduce the γd dispersive components of surface free energy (mJ/m2)
opportunities for the interfacial interactions between foulant mole- NF nanofiltration
cules and membrane; more importantly, these adsorptive forces UF ultrafiltration
were dramatically decreased due to the low surface free energy of PES polyethersulfone
membranes. Therefore the fluorinated polyamide NF membranes PAN polyacrylonitrile
would be expected to minimize the adhesion propensity and PIP piperazine
facilitate the detachment of foulants from membrane surface. Ober TMC trimesoyl chloride
et al. [45] proposed that the lower surface free energy led to higher PFOA perfluorooctanoic acid
self-cleaning potential of the membrane, i.e., the higher the protein TETA triethylenetetramine
release. Our experimental data further revealed that the membrane HA humic acid
surface with perfluoroalkyl side-chains were likely to construct a BSA bovine serum albumin
low-adhesive membrane surface with desirable HA release prop- PA polyamide
erty, owing to the relatively weak interaction between low surface Fm-PA-n fluorinated polyamide NF membrane prepared
free energy surface and HA molecules. using surface fluorination of polyamide NF mem-
brane with fluorinated polyamine concentration of
m wt% and the reaction temperature of n 1C
4. Conclusions

To fabricate antifouling NF membrane with low surface free

energy, a new kind of fluorinated polyamine was synthesized and
grafted onto polyamide NF membrane surface using the acylation
reaction between the amine groups of fluorinated polyamine and the
carbonyl groups on polyamide NF membrane. The presence of
perfluoroalkyl groups on the NF membrane surfaces significantly
lowered the surface free energy from 60.0 to 44.4 mJ/m2. With the
incorporation of fluorinated polyamine, the total flux decline ratio
during BSA solution membrane separation process was decreased
from 25.9% of polyamide NF membrane to 8.0% of F1.0-PA-60
membrane and the total flux decline ratio during HA solution
membrane separation process was decreased from 22.5% of poly-
amide NF membrane to 11.8% of F1.0-PA-60 membrane. In particular,
all the model foulants adsorbed and deposited on the fluorinated
polyamide NF membrane surfaces could be readily washed away by
simple hydraulic washing. The flux recovery ratio during each
membrane separation process could reach the maximum value of

98.5%. These results indicated that grafting fluorinated polyamine
onto polyamide NF membrane surface could be an effective approach
to improve the antifouling property.
Acknowledgments
This research was financially supported by National Science
Fund for Distinguished Young Scholars (21125627), Tianjin Natural
Science Foundation (No. 13JCYBJC20500) and the Program of
Introducing Talents of Discipline to Universities (No. B06006).
Nomenclature
Jw1 water flux (L/(m2 h))
V volume of permeated water (L)
A membrane area (m2)
Δt operation time (h)
Jp foulant solution flux (L/(m2 h))
Jw2 water flux after washing (L/(m2 h))
References
[1] C. Jarusutthirak, S. Mattaraj, R. Jiraratananon, Influence of inorganic scalants
and natural organic matter on nanofiltration membrane fouling, J. Membr. Sci.
287 (2007) 138–145.
[2] H. Ivnitsky, D. Minz, L. Kautsky, A. Preis, A. Ostfeld, R. Semiat, C.G. Dosoretz,
Biofouling formation and modeling in nanofiltration membranes applied to
wastewater treatment, J. Membr. Sci. 360 (2010) 165–173.
[3] R. Malaisamy, D. Berry, D. Holder, L. Raskin, L. Lepak, K.L. Jones, Development
of reactive thin film polymer brush membranes to prevent biofouling,
J. Membr. Sci. 350 (2010) 361–370.
[4] P. Xu, C. Bellona, J.E. Drewes, Fouling of nanofiltration and reverse osmosis
membranes during municipal wastewater reclamation: membrane autopsy
results from pilot-scale investigations, J. Membr. Sci. 353 (2010) 111–121.
[5] A. Asatekin, A. Menniti, S. Kang, M. Elimelech, E. Morgenroth, A.M. Mayes,
Antifouling nanofiltration membranes for membrane bioreactors from
self-assembling graft copolymers, J. Membr. Sci. 285 (2006) 81–89.
[6] Y.C. Chiang, Y.Z. Hsub, R.C. Ruaan, C.J. Chuang, K.L. Tung, Nanofiltration
membranes synthesized from hyperbranched polyethyleneimine, J. Membr.
Sci. 326 (2009) 19–26.
[7] A.M. Klüpfel, F.H. Frimmel, Nanofiltration of river water-fouling, cleaning and
micropollutant rejection, Desalination 250 (2010) 1005–1007.
[8] M. Beyer, B. Lohrengel, L.D. Nghiem, Membrane fouling and chemical cleaning
in water recycling applications, Desalination 250 (2010) 977–981.
[9] W.J. Lau, A. Ismail, Polymeric nanofiltration membranes for textile dye
wastewater treatment: preparation, performance evaluation, transport mod-
elling, and fouling control—a review, Desalination 245 (2009) 321–348.
[10] B. Van der Bruggen, M. Mänttäri, M. Nyström, Drawbacks of applying
nanofiltration and how to avoid them: a review, Sep. Purif. Technol. 63 (2008)
251–263.
[11] RJ Petersen, Composite reverse osmosis and nanofiltration membranes, J.
Membr. Sci. 83 (1993) 81–150.
[12] E.M. Van Wagner, A.C. Sagle, M.M. Sharma, Y.H. La, B.D. Freeman.Surface,
modification of commercial polyamide desalination membranes using poly
(ethylene glycol) diglycidyl ether to enhance membrane fouling resistance, J.
Membr. Sci. 367 (2011) 273–287.
[13] J.S. Louie, I. Pinnau, I. Ciobanu, K.P. Ishida, A. Ng, M. Reinhard, Effects of
polyether–polyamide block copolymer coating on performance and fouling of
reverse osmosis membranes, J. Membr. Sci. 280 (2006) 762–770.
[14] Y. Mansourpanah, E.M. Habili, Preparation and modification of thin film PA
membranes with improved antifouling property using acrylic acid and UV
irradiation, J. Membr. Sci. 430 (2013) 158–166.
[15] H. Wu, B. Tang, P. Wu, Preparation and characterization of anti-fouling
β-cyclodextrin/polyester thin film nanofiltration composite membrane,
J. Membr. Sci. 428 (2013) 301–308.
[16] Q.F. An, W.D. Sun, Q. Zhao, Y.L. Ji, C.J. Gao, Study on a novel nanofiltration
membrane prepared by interfacial polymerization with zwitterionic amine
 Y. Li et al. / Journal of Membrane Science 455 (2014) 15–23
monomers, J. Membr. Sci. 431 (2013) 171–179.
[17] Q. An, F. Li, Y. Ji, H. Chen, Influence of polyvinyl alcohol on the surface
morphology, separation and anti-fouling performance of the composite
polyamide nanofiltration membranes, J. Membr. Sci. 367 (2011) 158–165.
[18] M.K. Chaudhury, G.M. Whitesides, Direct measurement of interfacial interac-
tions between semispherical lenses and flat sheets of poly (dimethylsiloxane)
and their chemical derivatives, Langmuir 7 (1991) 1013–1025.
[19] Q. Zhao, Y. Liu, C. Wang, S. Wang, H. Müller-Steinhagen, Effect of surface free
energy on the adhesion of biofouling and crystalline fouling, Chem. Eng. Sci.
60 (2005) 4858–4865.
[20] M.E. Callow, R.L. Fletcher., The influence of low surface energy materials on
bioadhesion-a review, Int. Biodeterior. Biodegrad. 34 (1994) 333–348.
[21] J.A. Callow, M.E. Callow., Trends in the development of environmentally
friendly fouling-resistant marine coatings, Nat. Commun. 2 (2011) 244.
[22] H.S. Sundaram, Y. Cho, M.D. Dimitriou, J.A. Finlay, G. Cone, S. Williams,
D. Handlin, J. Gatto, M.E. Callow, J.A. Callow, E.J. Kramer, C.K. Ober, Fluorinated
amphiphilic polymers and their blends for fouling release applications: the
benefits of a triblock copolymer surface, ACS Appl. Mater. Interfaces 3 (2011)
3366–3374.
[23] C.J. Weinman, J.A. Finlay, D. Park, M.Y. Paik, S. Krishnan, H.S. Sundaram,
M. Dimitriou, K.E. Sohn, M.E. Callow, J.A. Callow, D.L. Handlin, C.L. Willis, E.
J. Kramer, C.K. Ober., ABC triblock surface active block copolymer with grafted
ethoxylated fluoroalkyl amphiphilic side chains for marine antifouling/fouling
release applications, Langmuir 25 (2009) 12266–12274.
[24] S. Krishnan, R. Ayothi, A. Hexemer, J.A. Finlay, K.E. Sohn, R. Perry, C.K. Ober, E.
J. Kramer, M.E. Callow, J.A. Callow, D.A. Fischer, Anti-biofouling properties of
comblike block copolymers with amphiphilic side chains, Langmuir 22 (2006)
5075–5086.
[25] M.D. Dimitriou, Z. Zhou, H.S. Yoo, K.L. Killops, J.A. Finlay, G. Cone, H.
S. Sundaram, N.A. Lynd, K.P. Barteau, L.M. Campos, D.A. Fischer, M.E. Callow,
J.A. Callow, C.K. Ober, C.J. Hawker, E.J. Kramer., A general approach to
controlling the surface composition of poly(ethylene oxide)-based block
copolymers for antifouling coatings, Langmuir 27 (2011) 13762–13772.
[26] Y Wang, D.E. Betts, J.A. Finlay, L. Brewer, M.E. Callow, J.A. Callow, D.E Wendt, J.
M. DeSimone, Photocurable amphiphilic perfluoropolyether/poly(ethylenegly-
col) networks for fouling-release coatings, Macromolecules 44 (2011)
878–885.
[27] Y. Wang, L.M. Pitet, J.A. Finlay, L.H. Brewer, G. Cone, D.E. Betts, M.E. Callow, J.
A. Callow, D.E. Wendt, M.A. Hillmyer, J.M. DeSimonea, Investigation of the role
of hydrophilic chain length in amphiphilic perfluoropolyether/poly(ethylene
glycol) networks: towards high-performance antifouling coatings, Biofouling
27 (2011) 1139–1150.
[28] Y. Cho, H.S. Sundaram, J.A. Finlay, M.D. Dimitriou, M.E. Callow, J.A. Callow, E.
J. Kramer, C.K. Ober, Reconstruction of surfaces from mixed hydrocarbon and
PEG components in water: responsive surfaces aid fouling release, Biomacro-
molecules 13 (2012) 1864–1874.
[29] H.S. Sundaram, Y. Cho, M.D. Dimitriou, C.J. Weinman, J.A. Finlay, G. Cone, M.
E. Callow, J.A. Callow, E.J. Kramer, C.K. Ober, Fluorine-free mixed amphiphilic
23
polymers based on PDMS and PEG side chains for fouling release applications,
Biofouling 27 (2011) 589–602.
[30] Y. Cho, D. Cho, J.H. Park, M.W. Frey, C.K. Ober, Y.L. Joo, Preparation and
characterization of amphiphilic triblock terpolymer-based nanofibers as anti-
fouling biomaterials, Biomacromolecules 13 (2012) 1606–1614.
[31] X. Zhu, H.E. Loo, R. Bai., A novel membrane showing both hydrophilic and
oleophobic surface properties and its non-fouling performances for potential
water treatment applications, J. Membr. Sci. 436 (2013) 47–56.
[32] W. Chen, Y. Su, J. Peng, Y. Dong, X. Zhao, Z. Jiang, Engineering a robust,
versatile amphiphilic membrane surface through forced surface segregation
for ultralow flux-decline, Adv. Funct. Mater. 21 (2011) 191–198.
[33] W. Chen, Y. Su, J. Peng, X. Zhao, Z. Jiang, Y. Dong, Y. Zhang, Y. Liang, J. Liu,
Efficient wastewater treatment by membranes through constructing tunable
antifouling membrane surfaces, Environ. Sci. Technol. 45 (2011) 6545–6552.
[34] X. Zhao, Y. Su, Y. Li, R. Zhang, J. Zhao, Z. Jiang, Engineering amphiphilic
membrane surfaces based on PEO and PDMS segments for improved anti-
fouling performances, J. Membr. Sci. 450 (2014) 111–123.
[35] X. Zhao, Y. Su, W. Chen, J. Peng, Z. Jiang, Grafting perfluoroalkyl groups onto
polyacrylonitrile membrane surface for improved fouling release property, J.
Membr. Sci. 415–416 (2012) 824–834.
[36] Y. Wang, Y. Su, Q. Sun, X. Ma, X. Ma, Z. Jiang, Improved permeation
performance of Pluronic F127–polyethersulfone blend ultrafiltration mem-
branes, J. Membr. Sci. 282 (2006) 44–51.
[37] D.Y. Kwok, The usefulness of the Lifshitz–van der Waals/acid–base approach
for surface tension components and interfacial tensions, Colloids Surf. A 156
(1999) 191–200.
[38] P.W. Morgan, S.L. Kwolek, Interfacial polycondensation. II. Fundamentals of
polymer formation at liquid interfaces, J. Polym. Sci. 40 (1959) 299–327.
[39] C.M. Magin, S.P. Cooper, A.B. Brennan., Non-toxic antifouling strategies, Mater.
Today 13 (2010) 36–44.
[40] S. Krishnan, C.J. Weinman, C.K. Ober, Advances in polymers for anti-biofouling
surfaces, J. Mater. Chem. 18 (2008) 3405–3413.
[41] Y.L. Ji, Q.F. An, Q. Zhao, W.D. Sun, K.R. Lee, H.L. Chen, C.J. Gao, Novel composite
nanofiltration membranes containing zwitterions with high permeate flux
and improved anti-fouling performance, J. Membr. Sci. 390–391 (2012)
243–253.
[42] M. Ulbricht, Advanced functional polymer membranes, Polymer 47 (2006)
2217–2262.
[43] B.D. McCloskey, H.B. Park, H. Ju, B.W. Rowe, D.J. Miller, B.J. Chun, K. Kin, B.
D. Freeman, Influence of polydopamine deposition conditions on pure water
flux and foulant adhesion resistance of reverse osmosis, ultrafiltration, and
microfiltration membranes, Polymer 51 (2010) 3472–3485.
[44] K. Khulbe, C. Feng, T. Matsuura., The art of surface modification of synthetic
polymeric membranes, J. Appl. Polym. Sci. 115 (2010) 855–895.
[45] H. Thérien-Aubin, L. Chen, C.K. Ober, Fouling-resistant polymer brush coat-
ings, Polymer 52 (2011) 5419–5425.