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a r t i c l e i n f o a b s t r a c t
Article history: Although several studies explored the use of nanoparticles as additives in membrane structures, mixed
Received 16 April 2011 matrix membranes still suffer from difculties in synthesis and applications. In this paper, a new outlook
Received in revised form 18 October 2011 on enhancement of membranes with nanoparticles is proposed by using ZnO as an alternative to TiO2 .
Accepted 21 October 2011
Although ZnO has attractive features that potentially could ll the objectives of mixed matrix membranes
Available online 25 October 2011
with lower cost and better performance, challenges in development remain. This paper investigates the
synthesis of ZnO enhanced membranes and evaluates the performance of mixed matrix membranes with
Keywords:
ZnO nanoparticles. Polyethersulfone (PES) membranes manufactured by diffusion induced phase inver-
Membranes
Nanoltration
sion in N-methyl-pyrrolidone (NMP) using a range of procedures were blended with ZnO nanoparticles
ZnO in a wide range of concentrations from ultralow to high (0.0354 wt%). It was shown that the new mem-
Membrane synthesis brane materials embedded with ZnO nanoparticles have signicantly improved membrane features. The
Nanoparticles inuence of the ZnO nanoparticles on the characteristics of PES/ZnO membranes was investigated with
microscopic observations, contact angle measurement, ltration experiments, fouling resistance deter-
mination and observation of the rejection of selected dyes. The results showed an overall improvement
compared to the neat membranes in terms of permeability as well as dye rejection and fouling resistance
by adding ZnO nanoparticles even in small and ultralow concentrations.
2011 Elsevier B.V. All rights reserved.
0376-7388/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2011.10.025
Author's personal copy
In this work, a new outlook on the use of nanoparticles in mem- dissolving different amounts of nanoparticles in the corresponding
brane structures is explored, through the use of zinc oxide (ZnO) volume of NMP for 3 h by mechanical stirring at 200 rpm and room
nanoparticles. ZnO is one of the most important multifunctional temperature. Eleven different concentrations of ZnO nanoparticles
semiconductor materials and exceptionally important for appli- were used: 0.035, 0.07, 0.085, 0.125, 0.250, 0375, 0.500, 0.750, 1, 2
cation in photo-catalysis and anti-bacterial materials, due to its and 4 wt%. Subsequently, the polymer was added to the solution,
excellent optical, electrical, mechanical and chemical properties which was stirred for 24 h at 500 rpm and 40 C. After formation of
[28]. The lower cost of ZnO and the increase of the surface-to- a homogenous solution, the lms were cast with 250 m thickness
volume ratio obtained when ZnO is used as particles in a nano-sized using a lmograph (K4340 Automatic Film Applicator, Elcometer)
scale make this alternative a potential system that can meet the in an atmosphere with controlled relative humidity on nonwoven
demand of an efcient and lower-cost device. polyester as support layer. Prior to the casting, the support layer
Furthermore, another issue that can limit the application of was wetted with NMP to prevent the polymer solution of intruding
nanoparticles is their toxicity since it is thought that nanoparti- in the pores of the support layer. The prepared lms were immersed
cles may persist as small particles in aquatic systems and that their in a non-solvent bath (distilled water at 20 C) for precipitation. The
bioavailability could be signicantly greater than that of larger membrane was afterwards repeatedly washed with distilled water
particles. For ZnO nanoparticles, positive conclusions have been to remove the remaining solvent, and stored wet. For each polymer
obtained [2933]. The use of nanoparticulate ZnO does not pro- solution composition, ve identical membrane sheets were made
duce an increase in toxicity since the size distribution and surface and tested to obtain an average value of ux and solute rejection.
area are not related to toxicity. Already in 2007 Franklin et al. [34]
compared the toxicity in algae of nanoparticulate ZnO, bulk ZnO 2.3. Characterization of the membrane surface
and ZnCl2 and observed that toxicity is attributable solely to dis-
solved zinc, this is, to simple solubility of the compounds since A contact angle measuring system DSA 10 Mk2 (Krss, Germany)
ZnO nanoparticles aggregate in freshwater systems forming ocs was used to measure the water contact angle of the synthesized
of even several microns with a saturation solubility similar to that membranes. A water droplet was placed on a dry at homogeneous
of bulk ZnO. Also, since ZnO nanoparticles will be embedded in a membrane surface and the contact angle between the water and
solid matrix (the membrane), a stable system can be developed, membrane was measured until no further change was observed.
keeping their physical properties associated to their size and the The average contact angle for distilled water was determined in
chemical activity related to their availability in the membrane. a series of 8 measurements for each of the different membrane
Thus, the use of ZnO in the nano-size scale incorporated in mem- surfaces. To visualize membrane surface characteristics, scanning
branes is a promising and novel system that may be the solution electron microscopy (SEM) measurements were performed. SEM
for the development of low-cost and fouling-prevention membrane images were made with a Philips XL30 FEG instrument with an
technology. accelerating voltage of 20 keV. Cross-sections were prepared by
The novelty of this paper is in the synthesis of ZnO enhanced fracturing the membranes in liquid nitrogen.
membranes in view to signicantly enhance the performance of
nanoltration technology in terms of permeation, rejection and
2.4. Filtration experiments
fouling resistance. The eventual membrane structure was also stud-
ied in this work.
The prepared membranes were characterized for water ux,
pure water permeability (membrane hydraulic resistance) and dye
2. Experimental rejection studies using dead end ltration experiments. Compar-
ison of the fouling-resistant ability of the manufactured neat and
2.1. Materials blended membranes was explored by cross-ow experiments.
Pure water permeability and dye rejection were determined for
Polyethersulfone (PES, type Radel) supplied by Solvay (Belgium) a wide range of membranes. Four membrane coupons of the same
was employed as the base polymer. 1-methyl-2-pyrrolidone (NMP, membrane sheet for eight membranes of each type were tested.
99.5%) was used as the polymer solvent. The support layer (Viledon Therefore, the obtained results are the average of 32 experimental
FO2471) used for the PES membrane manufacturing was obtained values. The maximum experimental errors were less than 5% and
from Freudenberg (Weinheim, Germany). ZnO nanoparticle and 8% for PES and PES/ZnO membranes, respectively.
humic acid (HA) were purchased from SigmaAldrich (St. Louis, The pure water ux was determined from a compaction exper-
MO). HA is known as a foulant in natural waters being fraction of iment at a transmembrane pressure of 10 bar and a constant
humic substances obtained from chemical and biological degrada- temperature of 25 C in dead-end mode with a Sterlitech HP4750
tion products from plant and animal residues [35]. Stirred Cell. A nitrogen cylinder coupled with the pressure regulator
Six different dyes were used to explore the size interaction was connected to the top of vessel to pressurize the cell. The active
in the interface solute-membrane pore. Organic compounds pur- membrane area was 14.6 cm2 . The thoroughly washed membrane
chased from Acros Organics (Belgium) were selected in order to was cut into the desired shape and tted in the dead end device. The
cover a large range of molecular mass. The selected dyes were volume of the appropriate solution was 250 mL. The initial water
methyl red (269.21 Da), neutral red (288.77 Da), methylene blue ux was measured 30 s after the pressurization. Permeate was col-
(319.85 Da), Sudan black (456.54 Da), Victoria blue (506.10 Da), lected in a graduated cylinder for a time interval until steady state
Congo red (696.67 Da). [36].
After compaction, the pure water permeability (PWP) was
determined by measuring the pure water ux (Jw ) at different trans-
2.2. Preparation of membrane
membrane pressures (P) from 2 to 14 bar; the slope of the linear
regression of the water ux as a function of transmembrane pres-
Neat PES membranes and ZnO-entrapped PES membranes
sure was determined as the permeability. The PWP was calculated
were prepared using phase inversion induced by immersion
by the following equation:
precipitation. PES cast from four different concentrations in N-
methyl-pyrrolidone (NMP) (25, 27, 30 and 32 wt%) was used as the Jw
PWP = (1)
polymer matrix. The ZnO-entrapped membranes were prepared by P
Author's personal copy
Fig. 1. SEM images of the surface of the synthesized membranes at different concentrations of ZnO (PES 27%) (A) Neat PES membrane, (B) 0.125 wt%, (C) 0.5 wt%, and (D)
0.7 wt%.
Author's personal copy
Fig. 2. Cross-sectional SEM images of synthesized PES (without ZnO) and PES/ZnO (0.125 wt% of ZnO) at different PES concentrations (A) 27% PES, (B) 30% PES, (C) 32% PES,
(D) 27% PES/ZnO, (E) 30% PES/ZnO, and (F) 32% PES/ZnO.
60
3.2. Hydrophilicity of membranes
75 70
27 wt.% PES
60
Permeability ( L h m bar )
-1
70
PES concentraon 27 wt.%
50
2
-1
Contact angle ()
65 40
30
60
20
55
10
0 0,035 0,07 0,0850,125 0,25 0,375 0,5 0,75 1 2 4
50
ZnO content (wt.%)
0 0,035 0,07 0,125 0,25 0,375 0,5 0,75 1 4
Fig. 6. Permeability of the newly synthesized membranes (L h1 m2 bar) in the
ZnO Concentraon (wt.%) ultralow to high concentration range for ZnO at 27 wt% of PES.
1.0
Humic acids 5mgL
-1 A
100
0.9
80 P = 10 bar
T = 25 C
Relave ux
0.8
Rejecon (%)
60
23 %
0.7 40
PES
0.6 PES/ZnO 0.035 ZnO wt.%
20 PES
PES/ZnO 0.125 ZnO wt.% PES/ZnO 0.125 ZnO wt.%
PES/ZnO 0.5 ZnO wt.% 0
0.5
0 5 10 15 20 25
300 400 500 600 700
Time (h)
Molecular weight (Da)
Fig. 7. Relative ux of PES membranes with four concentrations of ZnO nanoparti-
cles (0, 0.035, 0.125, and 0.5 wt%) in transient regime.
B 100
evidenced before. In addition, ZnO nanoparticles provide a remark- [19] Y.N. Yang, H.X. Zhang, P. Wang, Q.Z. Zheng, J. Li, Effect of TiO2 nanoparticles
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for blended membranes. This was observed even at unusually low ultraltration membrane modied by nano-sized alumina (Al2 O3 ) and its
concentration (0.035 wt%) of ZnO nanoparticles. antifouling research, Polymer 46 (2005) 77017707.
[21] X.C. Cao, J. Ma, X.H. Shi, Z.J. Ren, Effect of TiO2 nanoparticle size on the perfor-
mance of PVDF membrane, Appl. Surf. Sci. 253 (2006) 20032010.
Acknowledgements [22] L. Yan, Y.S. Li, C.B. Xiang, X.D. Shun, Effect of nano-sized Al2 O3 -particle addi-
tion on PVDF ultraltration membrane performance, J. Membr. Sci. 276 (2006)
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This research was supported by Basic Science Research Pro- [23] P. Jian, H. Yahui, W. Yang, L. Linlin, Preparation of polysulfoneFe3 O4 composite
gram through the National Research Foundation of Korea (NRF) ultraltration membrane and its behavior in magnetic eld, J. Membr. Sci. 284
funded by the Ministry of Education, Science and Technology (2006) 916.
[24] Y.N. Yang, P. Wang, Preparation and characterizations of a new PS/TiO2 hybrid
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membranes by solgel process, Polymer 47 (2006) 26832688.
port provided by the European Union, Romanian Government and [25] C.M. Wu, T.W. Xu, W.H. Yang, Fundamental studies of a new hybrid
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6/1.5/S/15. Arcadio Sotto would like to acknowledge the support
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