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Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l
a r t i c l e i n f o a b s t r a c t
Article history: Based on the existing carboxylic acid groups on surface of used commercial thin film composite polyamide
Received 24 January 2011 reverse osmosis membrane, two kinds of poly(ethylene glycol) derivatives with different chains were grafted
Received in revised form 1 March 2011 by carbodiimide-induced method to improve the antifouling property. The membranes before and after
Accepted 2 March 2011
modification were characterized by attenuated total reflectance Fourier transform infrared spectroscopy,
Available online 4 May 2011
scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy and static contact
Keywords:
angle measurement. Moreover, the water flux, NaCl rejection and fouling experiments were also conducted.
Polyamide reverse osmosis membrane The changes of chemical composition and morphology on membrane surfaces indicated the successful
Surface modification grafting of poly(ethylene glycol) derivatives. Compared to unmodified membrane, the modified membranes
Carboxylic acid groups were more resistant to fouling in protein and cationic surfactant feeding solutions. The method in this study
Carbodiimide-induced grafting provided a new way for surface modification of commercial polyamide reverse osmosis membranes.
Antifouling © 2011 Elsevier B.V. All rights reserved.
0011-9164/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2011.03.007
G. Kang et al. / Desalination 275 (2011) 252–259 253
ethy-3-(3-dimethyl amidopropyl) carbodiimide (EDC) has been used branes and confirm the grafting of PEG derivatives onto RO membrane
in organic synthesis [25] and chemical grafting [26,27]. Combining surface. The membrane samples were dried in vacuum oven before
with these two aspects, a surface modification method of commercial analysis. IR spectra of the membranes were recorded in the range of
thin film composite polyamide RO membrane by EDC-induced wavenumber 800–4000 cm− 1 at 25 °C.
grafting with hydrophilic PEG derivatives was developed in this
study. The chemical composition and morphology of membrane 2.3.2. SEM and AFM analyses
surface before and after modification were investigated using The surface morphology of unmodified and modified RO mem-
attenuated total reflectance Fourier transform infrared spectroscopy branes was observed by SEM (Philips XL30E) and AFM (Digital
(ATR-FTIR), X-ray photoelectron spectroscopy (XPS), scanning elec- Instruments Inc., Santa Barbara) using a Nanoscope III equipped with
tron microscopy (SEM) and atomic force microscopy (AFM). The 1553D scanner. The tapping mode in air was preferable and used to
performance and fouling resistance of modified and unmodified take AFM images [12]. The AFM images of 10 μm scans were acquired
membranes were also compared. by scanning the sample in air under ambient laboratory conditions at
a scan rate of 2 Hz. The roughness of the membrane surface was
2. Experimental assessed by measuring roughness parameters.
(b) ED600 and ED2001 ATR-FTIR spectroscopy can provide a convenient and effective way
H2N O to determine the composition of outmost part in a thin film composite
NH2
O RO membrane. It was performed in this study to confirm the successful
O
x y z grafting reaction of PEG chains onto membrane surface. Since the
CH3 CH3 CH3 thickness of polyamide barrier layer was about 0.2–0.3 μm [24], which
was thinner than the penetration depth of ATR-FTIR (about 0.5–1.0 μm)
Fig. 1. Chemical structure of (a) 1-ethy-3-(3-dimethyl amidopropyl) carbodiimide [12,29], the spectra of composite membranes showed characteristic
(EDC); (b) ED600 (x + z = 3.6, y = 9.0) and ED2001 (x + z = 6.0, y = 39.0). peaks of both polyamide layer (such as 1660 cm− 1 and 1544 cm− 1) and
254 G. Kang et al. / Desalination 275 (2011) 252–259
Fig. 2. Schematic diagram showing surface modification of polyamide RO membrane by EDC-induced grafting with PEG derivates.
polysulfone support membrane (such as 1584 cm− 1 and 1243 cm− 1). from 78 nm to 100 nm and 111 nm, respectively. The results were in
By comparing the IR spectrum between unmodified and modified agreement with those conducted by some other researchers. For
membranes in Fig. 3, the latter showed some new or intensity increased example, Van Wagner et al. observed a 19–33% increase in surface
peaks at 943 cm− 1, 1080 cm− 1 and 2875 cm− 1, which were ascribed to roughness upon modification with PEGDE [20]. Zou et al. grafted a
CH2 rock and C―C stretch, C―O and C―C stretch, and the CH2 PEG-like hydrophilic polymer (trimethylene glycol dimethyl ether)
symmetric stretch of PEG, respectively [30]. These results suggested that onto RO membrane by plasma polymerization and found that, the
the PEG derivatives were successfully immobilized onto the surface of roughness increased to 89.3 nm after 60 s treatment from 61.9 nm of
commercial RO membrane by carbodiimide-induced grafting method. the unmodified membrane [14].
The analytical results of SEM and AFM confirmed again that the
3.2. SEM and AFM analyses PEG chains were successfully grafted onto the surface of commercial
thin film polyamide RO membrane.
In order to examine the morphological changes of RO membranes
before and after surface modification, the SEM observations were 3.3. XPS analysis
conducted with a magnification of 2500 and 10,000. The images in
Fig. 4(a)–(f) presented the surface structure of unmodified mem- XPS is particularly well suited for examining the chemical
brane, ED600 modified membrane and ED2001 modified membrane composition of skin layer in RO composite membranes, and the
with different magnifications, respectively. It could be seen that some quantitative elemental composition of the top-most layer of mem-
new regular nodules appeared on modified membranes compared to brane sample can be calculated from XPS scanning spectrum. Table 1
the control membrane. Moreover, this phenomenon was more presented the atomic concentration data of unmodified membrane,
distinct for long-chain ED2001 than that of short-chain ED600. This ED600, ED600 modified membrane, ED2001 and ED2001 modified
was probably due to the connection or aggregation of grafted PEG membrane. Since ED600 and ED2001 contained higher oxygen and
chains in dry state. In order to more intuitively observe the stereo lower nitrogen, the increases in oxygen content and decreases in
structure of membrane surface, the AFM images were also performed. nitrogen content after modification were observed. Meanwhile, the
Fig. 5 showed the images of three-dimensional 10 μm scans for carbon content in ED600 and ED2001 was lower than that in
unmodified and PEG-modified RO membranes. As shown in Fig. 5(a), unmodified membrane, so the carbon content in modified mem-
the unmodified membrane exhibited a unique and characteristic branes decreased. Consequently, the ratio of O/C also increased. These
ridge-and-valley structure consistent with that in Ref. [24]. After trends have also been observed in our previous study [15] and by Van
surface grafting with PEG chains, some regions were covered with Wagner et al. [20].
new nodules. The similar morphological changes were also observed According to the membrane manufactures, the RO membrane
when PEG-like monomers were grafted onto RO membranes by sample used in this study was fully aromatic polyamide composite
plasma polymerization [14]. Meanwhile, the results showed an membrane. The polyamide was formed by an interfacial polymeriza-
increase in the roughness of membrane surface after modification, tion process based on TMC and MPD as shown in Fig. 6. Where, when
n = 1, the resulting polymer is fully crosslinked, giving a molecular
formula of C18H12N3O3. When n = 0, the resulting polymer is linear
ED2001 modified with pendant COOH, giving a molecular formula of C15H10N2O4 [3,29].
ED600 modified Therefore, the value of n in unmodified RO membrane could be
Unmodified obtained based on the data in Table 1 using Eqs. (3), (4) and (5):
1080cm-1
Oð%Þ 3n + 4ð1−nÞ 17:0
= = ð3Þ
Absorbance
Fig. 4. SEM micrographs of membranes before and after surface grafting.Unmodified: (a) × 2500, (b) × 10,000; ED600 modified: (c) × 2500, (d) × 10,000; ED2001 modified:
(e) × 2500, (f) × 10,000.
Meanwhile, the grafting rate of carboxylic acid (i.e., the proportion It could be calculated that x1 ≈ 0.74 and x2 ≈ 0.14. In other words,
of carboxylic acid reacted with PEG derivates) in modified membranes about 74% of carboxylic acid groups on RO membrane surface reacted
could be approximately estimated. The molecular formula of ED600 for ED600 modified membrane, but only about 14% for ED2001
and ED2001 were C31.8H67.6N2O12.6 and C99H202N2O45, respectively. If modified membrane. The significant difference of grafting rate for
x was the grafting rate of carboxylic acid, then 1 − x was the unreacted ED600 and ED2001 was probably due to their different chain lengths.
carboxylic acid groups. Based on the measured chemical composition Since the repulsion effect of initially grafted PEG chains in liquid
of modified membranes, the following equations could be obtained: surroundings would hinder the further grafting reaction around, the
ED600 modified membrane: ED2001 with longer molecular chain had more distinct steric effect,
resulting in lower grafting rate.
Oð%Þ 3 × 0:293 + 4 × 0:707 × ð1−xÞ + ð3 + 12:6Þ × 0:707 × x 21:2
= =
C ð%Þ 18 × 0:293 + 15 × 0:707 × ð1−xÞ + ð31:8 + 15Þ × 0:707 × x 70:5
3.4. Performance test
ð6Þ
The pure water flux and NaCl rejection of unmodified and PEG-
ED2001 modified membrane:
modified membranes were presented in Table 2. Similar to the
research results conducted by Belfer et al. [11] and Zou et al. [14], the
Oð%Þ 3 × 0:293 + 4 × 0:707 × ð1−xÞ + ð3 + 45Þ × 0:707 × x 22:0 surface modification by grafting in this study also caused decreases in
= = :
C ð %Þ 18 × 0:293 + 15 × 0:707 × ð1−xÞ + ð99 + 15Þ × 0:707 × x 70:3 water flux (decreased by about 35% in this study, and 36% in Ref. [11]
ð7Þ and 18% in Ref. [14] after modification for 60 min using methacrylic
256 G. Kang et al. / Desalination 275 (2011) 252–259
Fig. 5. Three-dimensional AFM images of unmodified and modified RO membranes: (a) unmodified; (b) ED600 modified; and (c) ED2001 modified. The size of images is
10 μm × 10 μm. The average roughnesses are: (a) 78 nm; (b) 100 nm; and (c) 111 nm.
G. Kang et al. / Desalination 275 (2011) 252–259 257
Table 1 Table 2
Chemical composition of grafting PEG derivatives, unmodified membrane and modified Pure water flux, salt rejection and static contact angle of membranes before and after
membranes (mol%). modification.
Sample C (%) O (%) N (%) O/C Membrane Pure water fluxa, Salt rejectionb, Static contact
(L/m2h) (%) angle (°)
ED600 (theoretical value) 68.5 27.2 4.3 0.399
ED2001 (theoretical value) 67.8 30.8 1.4 0.454 Unmodified membrane 50 ± 4 96.7 ± 0.4 53 ± 2
Unmodified membrane 72.5 17.0 10.5 0.234 ED600 modified membrane 32 ± 3 96.4 ± 0.2 42 ± 2
ED600 modified membrane 70.5 21.2 8.3 0.302 ED2001 modified membrane 36 ± 3 96.5 ± 0.4 38 ± 3
ED2001 modified membrane 70.3 22.0 7.7 0.312 a
Testing condition of pure water flux: deionized water, 1.05 MPa, 25 °C.
Totally crosslinked 75.0 12.5 12.5 0.167 b
Testing condition of salt rejection: 1500 ppm of NaCl solution, 1.05 MPa, 25 °C.
Linear with pendant COOH 71.5 19.0 9.5 0.266
COCl
H2N NH2
+
ClOC COCl
TMC MPD
O O O O
HN NH C C HN NH C C
C O C O
OH
NH n 1-n
NH
Fig. 6. Interfacial polymerization of commercial polyamide RO membrane dense layer based on TMC and MPD.
258 G. Kang et al. / Desalination 275 (2011) 252–259
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