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Journal of Membrane Science 387388 (2012) 4047

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Journal of Membrane Science


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

Antifouling enhancement of poly(vinylidene uoride) microltration membrane by adding Mg(OH)2 nanoparticles


Chunxu Dong a , Gaohong He a, , Hao Li a , Rui Zhao a , Yue Han a , Yulin Deng b
a State Key Laboratory of Fine Chemicals, R&D Center of Membrane Science and Technology, Dalian University of Technology, 2 Linggong Road, Dalian 116024, Liaoning Province, China b School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA 30332, USA

a r t i c l e

i n f o

a b s t r a c t
Mg(OH)2 nanoparticles were mixed into poly(vinylidene uoride) (PVDF) with PEG as an additive to prepare hybrid membrane by phase inversion. Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) measurements were performed, and the ultrasonic stability, porosity, hydrophilicity, permeation and bovine serum albumin (BSA) and Escherichia coli (E. coli) adsorption of the membrane were investigated. As revealed by FTIR spectra, large amount of OH groups were exist in the hybrid membrane due to the addition of Mg(OH)2 nanoparticles, and these OH groups are responsible for the hydrophilicity increase of the modied membrane. BSA and E. coli adsorption measurements conrm that hybrid membrane exhibited higher antifouling property than the original PVDF membrane, as the number of adsorbed proteins and bacterial cells on the membrane surface were reduced dramatically. PEG and Mg(OH)2 had mutual effects on the resulting structures and properties including porosity and permeability of the membrane. The superiority of the PVDF/Mg(OH)2 membrane in ltering bacterial solution was signicant, as the resistances with respect to time decreased dramatically with 10 wt.% Mg(OH)2 added, suggesting it would be very effective in preventing ux losses caused by biolm formation. 2011 Elsevier B.V. All rights reserved.

Article history: Received 10 June 2011 Received in revised form 4 October 2011 Accepted 7 October 2011 Available online 13 October 2011 Keywords: Hybrid membrane Antifouling Poly(vinylidene uoride) Mg(OH)2 nanoparticles Phase inversion

1. Introduction Poly(vinylidene uoride) (PVDF) is a well known polymer for its excellent chemical and oxidation resistance, and good physical and thermal stability. All these properties make PVDF an attractive membrane material for microltration [1], ultraltration [2], pervaporation [3] and membrane distillation [4]. However, due to its inherent hydrophobic characteristic, PVDF membrane often suffers serious ux losses due to membrane fouling. Membrane fouling, which is a severe problem for liquid membrane separations driven by pressure, limits the industrialization of the membrane technology. A number of novel strategies for fouling mitigation have emerged, including the use of additives [5], sludge granulation [6], hydrodynamic optimization [7], and membrane surface modication [8]. With the advent of nanotechnology, investigations on the effect of nanomaterials on biolms and fouling have been reported [9]. Fullerene C60 [10] and silver nanoparticles [11] have been studied for their interaction with the biolm. Recent works have also focused on blending inorganic nanomaterials to reduce irreversible membrane fouling, such as SiO2 [12],

Corresponding author. Tel.: +86 41184707892; fax: +86 41184707700. E-mail address: hgaohong@dlut.edu.cn (G. He). 0376-7388/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.memsci.2011.10.007

TiO2 [13], Al2 O3 [14] and so on, leading to an increase in membrane permeability and a better control of membrane surface properties. The phase inversion process is one of the most common methods in the preparation of synthetic polymeric membranes. The casting solution is cast as a thin lm and immersed into a non-solvent coagulation bath. Due to the exchange of solvent and non-solvent, phase separation of casting solution is induced to form polymerrich phase and polymer-lean phase, and the membrane is thereby obtained [15]. The additives in the casting solution affect the morphology and performance of the prepared membrane. Among them, polyethylene glycol (PEG) is known to promote pore formation in the polymeric membranes and thus enhance the permeation properties [1618]. Mg(OH)2 , often regarded as a good example of a material with structurally bound OH group, creates signicant interest in the role played by the OH groups [19]. It is an important and widely used inorganic ame retardant due to its environmental favored, readily available and low cost properties [20]. In our previous work, we found that Mg(OH)2 nanoplatelets were effective antibacterial agents against several bacteria and successfully prepared antibacterial paper [21,22]. In the present study, hydrophilic Mg(OH)2 nanoparticles were used as inorganic llers to prepare PVDF/Mg(OH)2 hybrid membrane by phase inversion method in order to prevent ux losses caused by membrane bio-fouling. The

C. Dong et al. / Journal of Membrane Science 387388 (2012) 4047

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2.3. Membrane characterizations 2.3.1. Fourier transform infrared spectroscopy (FTIR) study To investigate the chemical structures of the PVDF membrane, Mg(OH)2 nanoparticles and modied membrane, FTIR spectra were recorded with a Model EQUINOX 55 FTIR spectrophotometer (KBr pellet, Germany). 2.3.2. Morphology observation The surface and the cross-sectional morphologies of the membranes were viewed by a KYKY-2000B SEM under magnications ranging from 1500 to 50,000. The samples were freeze-fractured in liquid nitrogen to guarantee a sharp brittle fracture, and were successively sputter coated with a thin gold lm prior to SEM observation. 2.3.3. Porosity and hydrophilicity measurements The membrane porosity (%) was dened as the ratio between the volume of the pores and the total volume of the membrane. For porous membranes, it could be determined by gravimetric method, determining the weight of liquid (here pure water) contained in the membrane pores [23,24]: = (w1 w2 )/ w (w1 w2 )/ w + w2 / 100% (1)

Fig. 1. SEM picture of Mg(OH)2 nanoparticles.

hybrid membranes were characterized, and the effects of the additive of Mg(OH)2 nanoparticles were also discussed.

2. Experimental 2.1. Materials PVDF powder was purchased from General Electric Plastics (USA) and dried in a vacuum oven at 105 C for 10 h prior to be used. PEG with molecular weight of 600 Da, an additive as pore-former on the structure formation of membranes, was purchased from Damao Chemical Co. (Tianjin, China). Fig. 1 shows the scanning electron microscopy (SEM) image of Mg(OH)2 nanoparticles (also from Damao Chemical Co.), whose average size is about 350 nm 150 nm 25 nm. Dimethylacetamide (DMAc, reagent grade) was obtained from Fuyu Fine Chemical Co. (Tianjin, China). Hydrochloric acid (reagent grade) was purchased from Beijing Chemical Co. (Beijing, China). Bovine serum albumin (BSA) with molecular weight of 67,000 Da was purchased from Oboxing Company (Beijing, China). Escherichia coli (E. coli) BL-21 was provided by Bao biologic Co. (Dalian, China). Deionized (DI) water was used for preparing all solutions.

where w1 is the weight of the wet membrane (g), w2 is the weight of the dry membrane (g), w is the pure water density (0.998 g cm3 ) and m is the density of hybrid membrane, which was the average density of PVDF and Mg(OH)2 based on their each content in the membrane matrix. Membrane hydrophilicity was studied by measuring contact angle of the membrane at room temperature (Kruss, Model DSA10MK2). The deionized (DI) water was dropped on the top surface of the membrane sample at 5 different points, and the average of measured values was taken as its water contact angle. 2.3.4. Flux measurement A home-made ltration cell (effective area 33.18 cm2 , at 50 kPa) was used to measure the water ux of the membrane. The membrane was rst compacted for 20 min to minimize compaction effects. After the ux reached steady state, the ux was calculated with the following equation: J0 = V At (2)

2.2. Membranes preparation All the membranes were prepared by phase inversion method. PVDF was added into the binary mixture solvent of PEG and DMAc under magnetically stirring at 90 C until it dissolved completely. Here the PVDF/PEG/DMAc solution consisted of 13 wt.% PVDF, 510 wt.% PEG 600 [1618] and 8277 wt.% DMAc. Air bubbles in the casting solution were removed with a vacuum pump. The solution was cast directly upon the non-woven fabric as a supporting layer. Then the cast lm was immersed in a coagulant bath (ultraltration water, 25 C) where the polymer precipitated and the at membrane formed. While for the hybrid membrane, the Mg(OH)2 nanoparticles at the ratio from 10 to 20 wt.% to dry membrane were rstly dispersed into the binary mixture solvent of DMAc and PEG by an ultrasonator. The casting solution was used within 30 min after stirring in order to prevent the aggregation of Mg(OH)2 nanoparticles. All the membranes were kept in an aqueous bath for at least one day to remove solvents before used [18].

where J0 is the pure water ux (L m2 h1 ); V is the permeate volume (L); A is the membrane area (m2 ) and t is the time (h). For each membrane, 5 samples were tested and the water ux was the average value. 2.3.5. Protein and bacterium adsorption BSA (about 0.3 g/L) solution was prepared by DI water to carry out the static adsorption of protein on the membrane surface. The membrane samples were cut into small pieces (1 cm 7 cm) and were immersed in the BSA solution in test tubes (each for 13 mL) at room temperature (25 C) for 24 h to reach adsorption equilibrium, and all of the solutions before and after the BSA dissolution were approximately neutral (ranging from 7.38 to 7.54). The amount of BSA adsorbed on the membrane samples was calculated using initial and nal solutions of BSA concentrations measured by UVvis spectrometer (HP 8453) at the wavelength of 280 nm [25]. The membrane samples were immersed into E. coli-containing broth at room temperature for 24 h, and removed from bacterial suspension with sterile forceps and gently washed with phosphatebuffered solution (PBS). The mild ultrasonication for 10 min was used in order to dislodge the bacteria adhering to the membrane

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100
3699

5wt% PEG 10wt% PEG

567 1617

3446

Residual weight, wt %
4000

95 90 85 80 75 70 0 10

Adsorption

(a) (b) (c)

500

1000

1500

2000

2500

3000

3500

Wave numbers, cm-1


Fig. 2. FTIR spectra of (a) Mg(OH)2 nanoparticles, (b) hybrid membrane with 10 wt.% Mg(OH)2 and (c) PVDF membrane.

20

Mg(OH)2 content,wt %
surfaces, but to retain the adsorbed ones. The membranes were then immersed into a 3 vol.% glutaraldehyde in PBS for 4 h, followed by step dehydration with 50%, 70%, 90% and 100% ethanol for 10 min each for the bacterial xation [26]. The membranes were dried under vacuum and gold sputter-coated before SEM observation. 3. Results and discussion 3.1. Chemical components of the hybrid membrane The FTIR spectra of Mg(OH)2 nanoparticles, the PVDF/10 wt.% Mg(OH)2 hybrid membrane and the pure PVDF membrane are presented in Fig. 2. It can be seen that the spectrum of the modied membrane (b) contains an absorbance at 567 cm1 and a strong and sharp absorbance at 3699 cm1 assigning to the stretching vibration of MgO and OH bands respectively in Mg(OH)2 nanoparticles the same as those shown in (a), which are absent in (c). While the strong and broad absorbance bands at 1617 cm1 and 3446 cm1 of curve (a) are assigned to HOH bending vibrations and OH stretching vibrations of the crystal water on the Mg(OH)2 sample. This gure suggests that Mg(OH)2 nanoparticles were successfully added into the membrane by phase inversion method. Since there is no evidence for the chemical bonding between Mg(OH)2 and PVDF in both the previously published literatures and the present work, the combination is mainly because the Mg(OH)2 nanoparticles are embedded among the chains of PVDF. 3.2. Content of Mg(OH)2 nanoparticles in the membrane matrix To investigate the content of Mg(OH)2 nanoparticles in membrane matrix and their binding strength, the dried weights of membranes with 0%, 10% and 20 wt.% Mg(OH)2 nanoparticles were measured before and after the treatment both by diluted hydrochloric acid and ultrasonic vibration. Fig. 3 shows the residual weight of membranes after immersed into 0.2 mol/L HCl solution for 24 h. One can see that almost all the Mg(OH)2 nanoparticles added were held in the hybrid membrane matrix, suggesting that the phase inversion method is effective to produce the PVDF/Mg(OH)2 hybrid at membrane. Membranes were also subjected to ultrasonic irradiation for different time at the power level of 120 W, and the residual weight as a function of ultrasonication time was determined. The results are shown in Fig. 4. It is found that the weights of the membranes were still above 99.7% after 60-min high ultrasonic irradiation, suggesting that the Mg(OH)2 nanoparticles could be held tightly in the membranes matrix even under a strong mechanical irradiation.
Fig. 3. Residual weight of hybrid membrane after HCl treatment.

3.3. BSA and E. coli adsorption on the membrane surface To investigate the antifouling property of the hybrid membrane, the BSA and E. coli adsorption on membrane surface were investigated. Fig. 5 shows the results of static BSA adsorption on the membrane surface with different Mg(OH)2 contents. It can be seen that the unmodied PVDF membrane had higher amount of BSA adsorption than the modied membrane did, and higher Mg(OH)2 content gave lower BSA adsorption. Fig. 6 shows the SEM results of static E. coli adsorption of membranes with 0 and 20 wt.% Mg(OH)2 nanoparticles. One can see that there are many bacterial cells gathered on the surface of the pure PVDF membrane; while there are few bacterial cells absorbed on the surface of the membrane with 20 wt.% Mg(OH)2 nanoparticles. Both results suggest that the added Mg(OH)2 nanoparticles inhibited the biolm formation on the membrane surface, and the antifouling property may thereby be enhanced. 3.4. Morphology of membranes The formation of the membrane structure can be explained by mechanisms of coagulation process [27]. In the coagulation process, phase separation occurs quickly on the surface and the dense skin layer is formed. The water keeps on penetrating into the solution

100 98 96

Residual wight, %

0wt% Mg(OH)2
94 92 90 0 10 20 30 40 50 60

10wt% Mg(OH)2 20wt% Mg(OH)2

Untrasonic time, min


Fig. 4. Residual weight of hybrid membrane after ultrasonic treatment.

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120

BSA adsorption amounts, ug/cm 2

100 80 60 40 20 0 0 10

5wt% PEG 10wt% PEG

water keeps on penetrating into the solution under the skin layer, the increased viscosity of casting solution by Mg(OH)2 lowers the precipitation and assists the formation of uniform cells in the membrane [28]. 3.5. Hydrophilicity of membranes The surface hydrophilicity could affect the ux and antifouling ability of a membrane. In general, the hydrophilicity is evaluated by water contact angle. However, for hydrophilic material, it is possible for the water droplet on a millimeter scale to penetrate into the bulk through large pores, which affects the measurement of contact angle, and thus the measured contact angle may not reect the real surface properties [23]. When PEG content was 5 wt.%, the pore size on the top surface of the membrane did not change obviously (Fig. 7ac), so the effects of penetrating could be ignored. The decreased contact angle with the addition of Mg(OH)2 nanoparticles reveals an improved hydrophilicity, which is shown in Fig. 9ac. As revealed by FTIR spectra, large amount of OH groups were generated due to the addition of Mg(OH)2 nanoparticles, and these OH groups would be responsible for the hydrophilicity increasing. When PEG content was 10 wt.%, the measured water contact angle increased with the increase of Mg(OH)2 content (Fig. 9bd). Since there were some larger pores in the original unmodied membrane than the modied ones with Mg(OH)2 (Fig. 7d), this increase may be attributed to the less serious penetrating of the test water droplet. As the large pores reduced with Mg(OH)2 nanoparticles added (Fig. 7e and f), the top surface of the membrane became much smoother, leading to a relatively larger water contact angle. 3.6. Porosity of membranes The effect of Mg(OH)2 contents in the casting solution on porosity of the prepared membrane is presented in Fig. 10, and the results differ with different PEG content. The existence of PEG causes an increased porosity of the prepared membrane, and membranes of 10 wt.% PEG had a higher porosity than those of 5 wt.% PEG. When the Mg(OH)2 nanoparticles were mixed, the porosity decreased dramatically, suggesting that there were a lot of nanoparticles trapped in the pores and reduced the pore volumes. While for the lower PEG content (5 wt.%), the porosity did not decrease obviously, revealing that the added Mg(OH)2 nanoparticles were mainly dispersed in the polymer. It is concluded that the content of PEG has signicant inuence on the dispersion of Mg(OH)2 nanoparticles in

20

Mg(OH) 2 content, wt%


Fig. 5. BSA adsorption of membranes with different Mg(OH)2 nanoparticles content.

under the skin layer, and liquidliquid phase separation occurs, leading to the various membrane structures. The SEM images of the top surface of PVDF and PVDF/Mg(OH)2 membranes are shown in Fig. 7. It can be seen that the number of pores on the membrane surface increased with the addition of Mg(OH)2 nanoparticles, and the large pores greatly reduced and even disappeared. It is assumed that the Mg(OH)2 nanoparticles are dispersed uniformly in the casting suspension. During phase inversion, the hydrophilic nanoparticles have a high tendency to adsorb water, which contributes to more sites for water penetration, leading to more pores formed on the skin layer of the membrane. In addition, the high viscosity of the casting solution resulted from the added Mg(OH)2 nanoparticles may limit the enlargement of pores on the skin layer, especially when the PEG content is high (Fig. 7de). The cross-section morphologies of PVDF and PVDF/Mg(OH)2 membranes (PEG = 10 wt.%) are shown in Fig. 8, and it is the same trend for 5 wt.% PEG. There seems to be more macrovoids in hybrid membrane (b) than original PVDF membrane (a), and the modication also resulted in a formation of sponge-like structure at the bottom of the membrane matrix. It is suggested that the addition of hydrophilic Mg(OH)2 nanoparticles improves the water penetrating rate during coagulation process, which contributes to the formation of macrovoids in the membrane matrix. When the

Fig. 6. E. coli adsorption of membranes without (a) and with 20 wt.% (b) Mg(OH)2 nanoparticles.

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Fig. 7. Top surface morphologies of membranes with 0 wt.% (a and d), 10 wt.% (b and e), and 20 wt.% (c and f) Mg(OH)2 nanoparticles (ac for PEG = 5 wt.%; df for PEG = 10 wt.%).

Fig. 8. The cross-section morphologies of (a) PVDF and (b) 10 wt.% Mg(OH)2 /PVDF membranes (PEG = 10 wt.%).

Fig. 9. Water contact angles of membranes with 0 wt.% (a and d), 10 wt.% (b and e), and 20 wt.% (c and f) Mg(OH)2 nanoparticles (ac for PEG = 5 wt.%; df for PEG = 10 wt.%).

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90 85

700

10wt% PEG

Flux of E.coli solution, Lm h

5wt% PEG

600 500 400 300 200 100 0

20% Mg(OH)2 10% Mg(OH)2 0% Mg(OH)2

Porosity, %

80 75 70

65 60 0 10 20

-2

-1

10

20

30

40

50

60

70

80

Time, min
700
-2 -1

Mg(OH)2 content, wt%


Fig. 10. Porosity of membranes with different Mg(OH)2 nanoparticles content.

the hybrid membrane, and thereby Mg(OH)2 and PEG have a mutual effect on the membrane porosity. 3.7. Permeation properties of membranes It is well known that the ux and retention ratio are two critical factors to evaluate the performance of a membrane. In our work it has been found that the added MgOH2 has negligible effects on the retention ratio of the membrane, which is 24.00% and 24.54% for BSA both with 5% PEG before and after adding MgOH2 respectively, and all above 99.99% for E. coli; while the ux is always decreased dramatically by the membrane fouling. Therefore, the permeation of the original PVDF membrane and PVDF/MgOH2 was specically investigated as follows. The permeability of pure water through the membranes was evaluated and the results are compared in Fig. 11. Membranes with 10 wt.% PEG had higher water ux than those with 5 wt.% PEG, and the pure water ux values for the two membranes had the contrary trend by altering the concentration of Mg(OH)2 nanoparticles. These results reect the combination effect of the porosity and hydrophilicity changed by adding Mg(OH)2 nanoparticles. When the PEG content is high (10 wt.%), the PVDF membrane has a

Flux of E.coli solution, Lm h

600 500 400 300 200 100 0 0 10 20 30

20% Mg(OH)2 10% Mg(OH)2 0% Mg(OH)2

40

50

60

70

80

Time, min
Fig. 12. E. coli solution ux of membranes (a) PEG = 5 wt.%; and (b) PEG = 10 wt.%.

3500

5wt% PEG
3000

Pure water flux, Lm h

-1

10wt% PEG

2500 2000 1500 1000 500 0 0 10 Mg(OH) 2 content, wt% 20

relatively high porosity and permeability. As the Mg(OH)2 nanoparticles are mixed, many nanoparticles may be trapped in the original pores, which causes the porosity to decrease dramatically, thereby leading to a reduced permeability. While for the lower PEG content (5 wt.%), the added Mg(OH)2 nanoparticles may mainly dispersed in the polymer since the porosity does not decrease obviously, and the improved hydrophilicity by the addition of Mg(OH)2 nanoparticles contributes to an increased permeability of membrane. To investigate the permeation property of bacterial solution, after the pure water uxes, an E. coli solution permeation process was conducted. The E. coli solution ux of the membrane is shown in Fig. 12. Compared among the curves in Fig. 12a, it can obviously be seen that the modied membranes had better performance than that of the unmodied one, and the steady ux was improved by as much as 4 times with the addition of 20 wt.% Mg(OH)2 nanoparticles. As for Fig. 12b, even the initial permeate uxes of modied membranes were lower than the ux of the original membrane, however, with time passed by, the advantage of the modied membranes became more and more signicant. To further intuitively prove the superiority of the modied membrane dealing with the bacterial solution, the resistances during ux decline with respect to time were calculated according to the resistance model [29]. For dead-end membrane ltration, the permeate ux is: J= P (Rm + Rc ) (3)

Fig. 11. Pure water ux of membranes with different Mg(OH)2 nanoparticles content.

-2

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C. Dong et al. / Journal of Membrane Science 387388 (2012) 4047

40 35 30

RC , 10 m

25 20 15 10 5 0 0 10 20 30 40

0% Mg(OH)2 10% Mg(OH)2 20% Mg(OH)2

50

60

70

80

Time, min
12 10
-1

8 6

RC , 10 m

0% Mg(OH)2
4 2 0 0 10 20 30 40 50 60 70 80

hybrid membrane due to the addition of Mg(OH)2 nanoparticles, and these OH groups are responsible for the hydrophilicity increase of the modied membrane. BSA and E. coli adsorption measurements conrm that hybrid membrane exhibited the antifouling property. SEM results demonstrate a formation of sponge-like structure in the modied membrane matrix, and the pores on the surface appeared to be small and uniform, which may because the high tendency of the dispersed hydrophilic particles to adsorb water improving the water penetrating rate during coagulation process. When the PEG content is high (10 wt.%), the PVDF membrane has a relatively high porosity. As the Mg(OH)2 nanoparticles are mixed, many nanoparticles may be trapped in the original pores, which causes the porosity to decrease dramatically, thereby leading to a reduced permeability. While for the lower PEG content (5 wt.%), the added Mg(OH)2 nanoparticles may mainly dispersed in the polymer since the porosity does not decrease obviously, and the improved hydrophilicity by the addition of Mg(OH)2 nanoparticles contributes to an increased permeability of membrane. The superiority of the PVDF/Mg(OH)2 membrane in ltering E. coli solution was signicant, as the resistances with respect to time decreased dramatically with 10 wt.% Mg(OH)2 added, suggesting the hybrid membrane would be very effective in preventing ux losses caused by biolm formation. Further work will be done to investigate the mutual effects of different additives on the resulting structure of hybrid membrane, and optimal preparing conditions will be investigated. Acknowledgments We appreciate the nancial support of the National Science Fund for Distinguished Young Scholars of China, the Program for New Century Excellent Talents in Chinese Universities supported by the Education Ministry of China (NCET-06-0272), and the National Natural Science Foundation of China (20776026, 21006008). References
[1] Y. Chang, Y.J. Shih, R.C. Ruaan, A. Higuchi, W.Y. Chen, J.Y. Lai, Preparation of poly(vinylidene uoride) microltration membrane with uniform surface copolymerized poly(ethylene glycol) methacrylate and improvement of blood compatibility, J. Membr. Sci. 309 (2008) 165174. [2] W.D. Benzinger, B.S. Parekh, J.L. Eichelberger, High temperature ultraltration with Kynar poly(vinylidene uoride) membranes, Sep. Sci. Technol. 15 (1980) 11931204. [3] R.Y.M. Huang, R. Pal, G.Y. Moon, Pervaporation dehydration of aqueous ethanol and isopropanol mixtures through alginate/chitosan two polycomposite membranes supported by poly(vinylidene uoride) porous membrane, J. Membr. Sci. 167 (2000) 275289. [4] M. Khayet, T. Matsuura, Preparation and characterisation of polyvinylidene uoride membranes for membrane distillation, Ind. Eng. Chem. Res. 40 (2001) 57105718. [5] V. Iversen, R. Mehrez, R.Y. Horng, C.H. Chen, F. Meng, A. Drews, B. Lesjean, M. Ernst, M. Jekel, M. Kraume, Fouling mitigation through occulants and adsorbents addition in membrane bioreactors: comparing lab and pilot studies, J. Membr. Sci. 345 (2009) 2130. [6] X. Li, F. Gao, Z. Hua, G. Du, J. Chen, Treatment of synthetic wastewater by a novol MBR with granular sludge developed for controlling membrane fouling, Sep. Purif. Technol. 46 (2005) 1925. [7] Y. Liu, G. He, X. Liu, G. Xiao, B. Li, CFD simulations of turbulent ow in bafe-lled membrane tubes, Sep. Purif. Technol. 67 (2009) 1420. [8] D. Rana, T.G.B. Matsuura, Surface modications for antifouling membranes, Chem. Rev. 110 (2010) 24482471. [9] A. Drews, Membrane fouling in membrane bioreactors-characterisation, contradictions, cause and cures, J. Membr. Sci. 363 (2010) 128. [10] S. Chae, S. Wang, Z.D. Hendren, M.R. Wiesner, Y. Watanabe, C.K. Gunsch, Effects of fullerene nanoparticles on Escherichia coli K12 respiratory activity in aqueous suspension and potential use for membrane biofouling control, J. Membr. Sci. 329 (2009) 6874. [11] J. Fabrega, J.C. Renshaw, J.R. Lead, Interactions of silver nanoparticles with pseudomonas putida biolms, Environ. Sci. Technol. 43 (2009) 90049009. [12] M. Khayet, J.P.G. Villaluenga, J.L. Valentinb, M.A. Lpez-Manchadob, J.I. Menguala, B. Seoanea, Filled poly(2,6-dimethyl-1,4-phenylene oxide)dense membranes by silica and silane modied silica nanoparticles: characterization and application in pervaporation, Polymer 46 (2005) 98819891.

-1

10% Mg(OH)2 20% Mg(OH)2

Time, min
Fig. 13. Cake resistances during ux decline of membranes (a) PEG = 5 wt.%; and (b) PEG = 10 wt.%.

where P is the transmembrane pressure (Pa), is the permeate viscosity (Pa S), Rm is the intrinsic membrane resistance (m1 ) and Rc is the cake resistance (m1 ). Since the values of P, and Rm remained constant during ltration in this work, the ux J depended greatly on the value of Rc . The values of Rc of all the membranes increased with respect to time as shown in Fig. 13, which may due to the biolm formation and pore blocking by bacteria. However, with the addition of Mg(OH)2 nanoparticles, the increase of Rc slowed down. There are several possible reasons for this alteration. Firstly, as Figs. 7 and 8 show, the pores became smaller due to the structure change and the nanoparticles block when Mg(OH)2 nanoparticles were added to the membrane. As a result, the number of E. coli entrapped in the pores was reduced. Secondly, E. coli entrapped in the pores might be killed by Mg(OH)2 nanoparticles through direct contact [21,22] and the died cells would depart from the membrane matrix. Lastly, the hydrophilicity of the hybrid membrane was improved with the addition of Mg(OH)2 nanoparticles, and the numbers of adsorbed bacterial cells were reduced. All of these may lead to less serious biolm formation and pore blocking, and the relative ux of the E. coli solution to pure water was thereby increased. 4. Conclusion Organicinorganic PVDF/Mg(OH)2 hybrid membrane with PEG as an additive was prepared by phase inversion process. As revealed by FTIR spectra, large amount of OH groups were exist in the

C. Dong et al. / Journal of Membrane Science 387388 (2012) 4047 [13] Y. Lu, H. Sun, L. Meng, S. Yu, Application of the Al2 O3 PVDF nanocomposite tubular ultraltration (UF) membrane for oily wastewater treatment and its antifouling research, Sep. Purif. Technol. 66 (2009) 347352. [14] Y.N. Yang, H.X. Zhang, P. Wang, Q. Zheng, J. Li, The inuence of nano-sized TiO2 llers on the morphologies and properties of PSF UF membrane, J. Membr. Sci. 288 (2007) 231238. [15] L. Zhang, G. He, W. Zhao, M. Tan, X. Li, Effect of formamide additive on the structure and gas permeation performance of polyethermide membrane, Sep. Purif. Technol. 73 (2010) 188193. [16] S. Wongchitphimon, R. Wang, R. Jiraratananon, L. Shi, C.H. Loh, Effect of polyethylene glycol (PEG) as an additive on the fabrication of polyvinylidene uoride-co-hexauropropylene (PVDF-HFP) asymmetric microporous hollow ber membranes, J. Membr. Sci. 369 (2011) 329338. [17] G. Arthanareeswaran, T.K. Sriyamuna Devi, D. Mohan, Development, characterization and separation performance of organicinorganic membranes Part II. Effect of additives, Sep. Purif. Technol. 67 (2009) 271281. [18] J. Kim, K. Lee, Effect of PEG additive on membrane formation by phase inversion, J. Membr. Sci. 138 (1998) 153163. s [19] P.T. Jochym, A.M. Ole , K. Parlinski, J. azewski, P. Piekarz, M. Sternik, Structure and elastic properties of Mg(OH)2 from density functional theory, J. Phys.: Condens. Matter 22 (2010) 445403. [20] J.Z. Liang, J. Yang, C.Y. Tang, Melt shear viscosity of PP/Al(OH)3 /Mg(OH)2 ame retardant composites at high extrusion rates, J. Appl. Polym. Sci. 119 (2011) 18351841.

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[21] C. Dong, J. Cairney, Q. Sun, O.L. Maddan, G. He, Y. Deng, Investigation of Mg(OH)2 nanoparticles as an antibacterial agent, J. Nanopart. Res. 12 (2010) 21012109. [22] C. Dong, D. Song, J. Cairney, O.L. Maddan, G. He, Y. Deng, Antibacterial study of Mg(OH)2 nanoplatelets, Mater. Res. Bull. 46 (2011) 576582. [23] H.M. Yu, C. Ziegler, M. Oszcipok, M. Zobel, C. Hebling, Hydrophilicity and hydrophobicity study of catalyst layers in proton exchange membrane fuel cells, Electrochim. Acta 51 (2006) 11991207. [24] J.F. Li, Z.L. Xu, H. Yang, Microporous polyethersulfone membranes prepared under the combined precipitation conditions with non-solvent additives, Polym. Adv. Technol. 19 (2008) 251257. [25] S. Boributh, A. Chanachai, R. Jiraratananon, Modication of PVDF membrane by chitosan solution for reducing protein fouling, J. Membr. Sci. 342 (2009) 97104. [26] C. Yao, X. Li, K.G. Neoh, Zhilong Shi, E.T. Kang, Surface modication and antibacterial activity of electrospun polyurethane brous membranes with quaternary ammonium moieties, J. Membr. Sci. 320 (2008) 259267. [27] K.N. Turhan, F. Sahbaz, A. Guner, A spectrophotometric study of hydrogen bonding in methylcellulose-based edible lms plasticized by polyethylene glycol, J. Food Sci. 66 (2001) 5962. [28] M.A. Frommer, R.M. Messalem, Mechanism of membrane formation. VI. Convective ows and large void formation during membrane precipitation, Ind. Eng. Chem. Prod. Res. Dev. 12 (1973) 328333. [29] Y. Lee, M.M. Clark, Modeling of ux decline during crossow ultraltration of colloidal suspensions, J. Membr. Sci. 149 (1998) 181202.

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