Desalination 278 (2011) 141149

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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

Pure sponge-like membranes bearing both high water permeability and high retention capacity
Zhenghui Wang, Jun Ma , Qianliang Liu
State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, National Engineering Research Center of Urban Water Resources, Harbin 150090, China

a r t i c l e

i n f o

a b s t r a c t
Porous poly(vinylidene uoride) (PVDF) membranes were prepared using phase inversion method. It was found that three pure sponge-like membranes could be generated using composite additive such as ferrous chloride/nano-silica, calcium chloride/nano-silica, and ferrous chloride/hydroxylamine hydrochloride. The generated sponge-like membranes all bear obviously higher water permeability and higher or little lower retention capacity compared with their counterpart macrovoid membranes, which were prepared using ferrous chloride or calcium chloride as additive. High magnication SEM (scanning electron microscopy) photos revealed the great differences between the two kinds of macroscopically similar sponge structures. The specic area (BET surface area), pore volume, and pore size distribution, measured using the nitrogen adsorptiondesorption method, indicated that the sponge-like membranes (X1, Y1, and Z1) are more porous and hold narrower (X1 and Z1) pore size distributions than their counterpart membranes. The trends revealed by the BET data agreed relatively well with the ux and retention data, thus implied that the N2 adsorptiondesorption method might be an effective means to investigate the structureproperty relationship of polymeric membranes. The comparison study indicates that the sponge-like membranes in this work have comparable and even better performance than some of the commercial PVDF membranes in terms of ux and retention. 2011 Elsevier B.V. All rights reserved.

Article history: Received 28 February 2011 Received in revised form 4 May 2011 Accepted 5 May 2011 Available online 1 June 2011 Keywords: Poly(vinylidene uoride) (PVDF) Membrane preparation Sponge Macrovoid Nitrogen adsorptiondesorption

1. Introduction Improving both the permeability and retention capacity of membranes for liquid separation such as drinking water purication always is a subject matter of membrane preparation [1,2]. In 1959, the rst applicable cellulose acetate reverse osmosis membrane was invented by Loeb and Sourirajan, using the phase inversion method with LiClO4 as additive. The invented membrane displayed an asymmetric structure, with an ultrathin dense top layer and a porous macrovoid sublayer. As a result, the water permeability of the membrane was largely improved [3]. Since then, extensive researches have been made on the formation of various asymmetric membrane structures and their permeationretention properties. According to most of the previous researches, membranes dominated by the macrovoid structure always are more permeable than those sponge ones [48]. So far, various methods have been explored to generate a proper macrovoid sublayer, especially for those low-pressure membranes such as the ultraltration and microltration membranes [414]. As for the preparation of PVDF membranes, the generally used additives to improve membrane performance include PVP [15], PEG [16], LiCl [6,10], LiClO4 [17],

Corresponding author. Tel.: + 86 451 86282292; fax: + 86 451 82368074. E-mail address: majun@hit.edu.cn (J. Ma). 0011-9164/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.desal.2011.05.023

ethylene glycol [18], water, ethanol, 1-propanol [9,19] etc. These additives modify the membrane structure mainly through inuencing the kinetics and thermodynamics of the formation process. In addition, it is generally observed that the retention capacity of the membrane would decrease when the permeability was improved, and vice versa [15,18,20]. The possible explanation for this phenomenon is given below. If the solventnonsolvent mutual diffusion in the immersionprecipitation process is very fast, it would benet the formation of a macrovoid sublayer. Meanwhile, the fast transport of solvent and nonsolvent, passing through the nascent surface layer, might promote the growth of the surface pores before the complete solidication of the surface layer [2124]. Thus, a more porous macrovoid sublayer is always accompanied with a less dense top surface layer. Expectably, the high permeability and low retention capacity would be generated by the combination of less dense top surface and macrovoid sublayer [25]. In this paper, we report several at sheet poly(vinylidene uoride) (PVDF) membranes prepared from different dope solutions using the phase inversion method. These membranes are pure sponge-like, however, they all bear obviously higher water permeability and higher or little lower retention capacity compared with their counterpart macrovoids dominated membranes. To the best of our knowledge, the formation of pure sponge-like PVDF membranes using N,N-dimethylacetamide(DMAc)/H2O as the solvent/nonsolvent pair, and pure sponge-like PVDF membranes bearing both high water

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permeability and high retention capacity simultaneously have been seldom reported, however, are very meaningful. 2. Experimental 2.1. Materials Poly(vinylidene uoride), obtained from Shanghai 3 F New Materials Co., Ltd. (FR904, Mn = 475,637, [] = 1.41.9 dL/g) was used as the membrane material. N,N-dimethylacetamide (DMAc, Tianjin Bodi Chemicals Co., Ltd. N99%, Analytical reagent) and distilled water (H2O) were used as solvent and coagulant respectively. Ferrous chloride, calcium chloride (FeCl24H2O, CaCl22H2O, Tianjin Bodi Chemicals Co., Ltd. Analytical reagent), and hydroxylamine hydrochloride (NH2OHHCl, Tianjin Chemical Reagent Company. Analytical reagent) were used as the salt additives. Nano-silica (size: 2040 nm, hydroxyls on the silica surface make it hydrophilic, obtained from Zibo Haina High Technology Co., Ltd.) was used to dope the casting solution. Trypin (Mw = 23,000 g/mol), Pepsin (Mw = 35,000 g/mol), and BSA (Mw = 68,000 g/mol) used in the retention experiment were purchased from Beijing Solarbio Science & Technology Co., Ltd, DongWu Bio-Chemical Products Company in Su Zhou, and Sinopharm Chemical Reagent Co., Ltd, respectively. All the materials were used as received. 2.2. Membrane preparation The membranes were prepared using the phase inversion method. Dope solutions with different contents of PVDF, DMAc, and additive (s) were prepared, with their compositions and viscosities at 40 C shown in Table 1. The homogeneous solutions were uniformly cast on the glass plates with a home-made glass knife at room temperature (15 1 C). After 20 s evaporation in the air (Relative humidity ranged from 20% to 45%), they were immediately immersed into the distilled water (25 C). The subsequently detached lms were removed into another distilled water container and kept for 3 days to remove the residual solvent. Then certain areas of each membrane were taken out and subjected to the pure water ux test and pepsin retention measurement, with the left membranes immersed into ethanol for 12 h. After that, the membranes were dried in air. The dry membranes would undergo SEM analysis and N2 adsorption desorption experiment for the BrunauerEmmettTeller (BET) surface area analysis and BarrettJoynerHalenda (BJH) pore size distribution analysis. 2.3. Membrane characterization 2.3.1. Scanning electron microscopy (SEM) analysis Firstly, the dry membrane samples were immersed in liquid nitrogen and carefully fractured which would give a generally clean break (for cross-section observation). Then, the specimens including those for surface observation were xed on a metal support and sputtered a layer of gold with proper thickness under vacuum. After
Table 1 The compositions of different dope solutions (weight proportion) and their viscosity at 40 C. Membrane ID X X1 Y Y1 Z Z1 PVDF 18 18 18 18 19 19 DMAc 78 74 78 74 77 77 Additive1 4(FeCl24H2O) 4(FeCl24H2O) 4(CaCl22H2O) 4(CaCl22H2O) 2(FeCl24H2O) 2(FeCl24H2O) Additive2 0 4(SiO2) 0 4(SiO2) 0 2(NH2OHHCl) Dope viscosity (Pas) 22.5 66.5 34 N 100 29 32.5

that the membrane morphology were examined using a scanning electron microscope (SEM, Phillip's SEM model FEI. Sirion 200, Netherlands). 2.3.2. Pure water ux test Pure water uxes of the membranes were determined using a membrane testing unit (Shanghai Mosu Scientic Equipment Co., Ltd, China). The wet membrane sheets were cut into circles of 31.5 mm in diameter and subsequently installed into the testing unit. Firstly, the trans-membrane pressure was set at 0.2 MPa (supplied by nitrogen gas), after 20 min of distilled water (18 C) permeation the ux was practically constant, then the trans-membrane pressure was restored to 0.1 MPa after which 1-min permeate was collected to calculate the pure water ux. 2.3.3. Protein retention measurement For one piece of membrane sample, after the measurement of pure water ux, protein solution (200 ppm, 18 C) was fed into the testing unit. Then the feed solution was vigorously stirred (360 r/min for the at sheet membranes while 0.700.95 m/s for the hollow ber membranes), and was driven through the membrane under 0.1 MPa for 15 min. After that, the sample was collected, and a relatively steady protein concentration of the permeate was used to calculate the rejection. The percentage rejection (R) can be calculated according to the formula: R% = 1Cp = Cf where Cf and Cp denote the protein concentration in the feed and permeate respectively. Protein concentration was determined by a UVvisible spectrophotometer (UV-2550, Shimadzu) at 280 nm. All the reported ux and retention values were expressed by the average of three sample measurements for each casting condition. 2.3.4. BET analysis The specic area (BET surface area, SBET) and pore size distribution of the membrane samples were measured using the nitrogen adsorptiondesorption method on an ASAP 2020V3.00H apparatus. The SBET was determined from the linear part of the BET curve, the pore size distribution was calculated from the desorption branch of N2 adsorptiondesorption isotherms using the BJH approach. All the samples were degassed at 65 C for 8 h prior to the measurement. 3. Results and discussion 3.1. Morphology of the membranes The cross-section morphologies of the membranes were presented in Fig. 1. As shown by Fig. 1(a) and (b), the bulk structure of membrane shifted from macrovoid-sponge composite (membrane X) to pure sponge (membrane X1) when the additive changed from sole ferrous chloride to ferrous chloride/nano-silica (Table 1). Similar changes of structure can be observed from membrane Y Y1 and ZZ1 as shown by Fig. 1(c)(d) and (e)(f), respectively. The possible explanation for the formation of pure sponge structure is given below. The addition of additive2 (e.g. nano-SiO2, NH2OHHCl) increased the viscosity of dope solution (Table 1) [26], expectably, the increase of dope viscosity would accordingly increase the resistance of solventnonsolvent mutual diffusion in the immersionprecipitation process. Thus, the macrovoid structure formation was suppressed [23]. While for membrane Z1, the small increase of dope viscosity seems not the only reason for the formation of sponge-like structure. Additional possible reasons should be taken into account. On one hand, the addition of hydroxylamine hydrochloride in casting solution would reduce the chemical potential thus the activity of solvent. Accordingly, the out-diffusion

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Fig. 1. Cross-section morphology of the membranes: (a) X, (b) X1, (c) Y, (d) Y1, (e) Z, (f) Z1.

of solvent will be suppressed. On the other hand, hydroxylamine hydrochloride as a strong reductant might be oxidized in the dissolving process (the mixture container was not strictly sealed at this stage). Water will be generated in oxidizing hydroxylamine hydrochloride, its formation will not only suppress the in-diffusion of nonsolvent but also decrease the thermodynamic stability of the casting solution. All these behaviors would suppress the formation of macrovoid structure and benet the formation of sponge-like structure.

3.2. Pure water ux and pepsin retention of the membranes As shown in Fig. 2, membrane X1, Y1, and Z1 exhibit obviously higher pure water ux than their counterpart macrovoids dominated membrane X, Y, and Z, respectively. In addition to the higher pure water ux, Fig. 3 showed that membrane X1, Y1, and Z1 also bear higher or little lower pepsin retention compared with their counterpart membranes. In fact, the higher pepsin retention of membrane Z1 than that of membrane Z is consistent with the SEM photos shown in

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240

200 160 120 80 40 0 X X1 Y Y1 Z Z1

Membrane ID
Fig. 2. Pure water ux of the membranes.

structures seems related to a nucleation and growth mechanism [27,28], and related to the suppressed solventnonsolvent mutual diffusion in terms of kinetics. A systematic study on the formation mechanism will be carried out in our subsequent work. Moreover, the upmost parts of membrane cross-sections (X, X1, Y1, Z1) were also shown in Fig. 5. It seems that the very parts beneath the surface layer of membrane X1, Y1, and Z1 (Fig. 5(b1), (c1), and (d1)) are more porous than that of membrane X (Fig. 5(a1)), this may also contribute to the higher ux of membrane X1, Y1, and Z1. In addition to structure, the thickness of membranes (X 57.2 m, X1 57.8 m; Y 52.5 m, Y1 73.7 m; Z 59.2 m, Z1 53.8 m. Each value was the average of ve different position SEM measurements) also would inuence the ux. Though the lower thickness of membrane Z1 would contribute to its higher ux (compared with membrane Z), the higher thicknesses of membrane X1 and Y1 and their obvious higher ux (compared with membrane X and Y, respectively) imply that it is more reasonable to attribute the ux difference of these membranes to their structures, which have been discussed above. 3.3. BET surface area (SBET) and pore size distribution of the membranes In order to get further information on the membrane pore structure and thus try to reveal the real cause of the special structureproperty relationship observed in this work, the N2 adsorptiondesorption method was employed. The BET surface area (SBET), BJH Desorption cumulative volume of pores (between 1.700 nm and 300,000 nm in diameter, VBJH), and BJH Desorption average pore diameter (DBJH) of the membranes were shown in Table 2, the pore size distributions were presented in Fig. 6. Table 2 shows that each SBET value of the sponge-like membranes is obviously higher than that of its counterpart membrane. In general, the higher SBET value implies a more porous structure, and more porous structure might be more permeable. In this context, a relatively good correlation can be found between the ux data (Fig. 2) and the SBET values (Table 2). Similarly, VBJH value also reects porosity, in Table 2, each VBJH value of membrane X1, Y1, and Z1 is also higher than that of its counterpart membrane (it should be mentioned here that most cellular pores and macrovoid pores were not measured because their sizes are out of the coverage of this method). However, membranes Z and Z1 displayed small difference on their VBJH values though they hold quite different SBET values (the real cause is still not very clear). As for DBJH, since the obtained values are the average of entire pores but not just those in surface layer, so we prefer to try to correlate DBJH values with ux rather than with retention. It can be found from Table 2 and Fig. 2 that the larger the average pore size, the higher the membrane ux, however, membrane ZZ1 again showed an exception. Though, in theory, the N2 adsorptiondesorption method measured the pore size distribution of the entire sample, whether or to what extent this method can reect the real information on the surface pore structure still lacks a solid conclusion. In this work, we try to seek useful information from the pore size distribution curves and attempt to correlate them with the pepsin retention data. Since the surface pore size of ultraltration membrane is always less than 100 nm, Fig. 6 only displayed the distribution of those pores less than 100 nm in size. Fig. 6(a) and (b) showed that the peaks of the two distribution curves both situated at about 37 nm, however, the pore size distribution of membrane X1 is obviously narrower. It seems reasonable to attribute the higher pepsin retention of membrane X1 (Fig. 3) to the similar peak pore size of the two membranes while narrower pore size distribution of membrane X1. Fig. 6(c) and (d) showed that the peaks of the two distribution curves situated at about 45 nm and 55 nm, respectively. Moreover, the distribution curve of membrane Y1 is broader than that of membrane Y. It is supposed that the bigger peak pore size and broader pore size distribution resulted in the lower pepsin retention of membrane Y1 (compared with

Fig. 4, which indicates that the surface of membrane Z1 is denser (or less defective) than that of membrane Z though the non-defective parts (shown by Fig. (a3) and (b3)) of the two membranes are nearly same dense (other SEM photos, which indicated that the surface structure comparisons of membrane XX1 and YY1 are similar to that of membrane ZZ1, were not shown here). In general, the pure water ux depends largely on the surface structure and bulk structure of the membrane. The obviously higher pure water ux and denser surface layer of membrane X1, Y1, and Z1, compared with membrane X, Y, and Z, respectively, implied that the sponge structure of the former three membranes should be more permeable than that of the latter three ones, respectively. In order to make a test for this speculation, the SEM photos of the sponge structures and upmost part of cross-sections of membrane X, X1, Y1, and Z1 were shown in Fig. 5 (the sponge structures of membrane Y and Z are quite similar to that of membrane X, so they were not shown here). Fig. 5(a) displayed the very traditional sponge structure, which was composed of many cellular pores, those pores were isolated with many dense walls if not totally closed. Generally, this kind of structure would be highly resistant [46]. Compared with Fig. 5(a), (b)(d) displayed the quite different sponge structures. Though some differences also existed among the sponge structures of membrane X1, Y1, and Z1, it can be found that the cellular pores of these three sponge structures all are very interconnected, even having no obvious isolating walls. We believe it was this kind of special sponge structure that made membrane X1, Y1, and Z1 more permeable than membrane X, Y, and Z, respectively. The formation of such permeable sponge

Pure water flux (Lm-2h-1)

Rejection (pepsin 35K, %)

90

80

70

60 X X1 Y Y1 Z Z1

Membrane ID
Fig. 3. Pepsin retention of the membranes.

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Membrane Z

Membrane Z1

(a1, 5K)

(b1, 5K)

(a2, 15K)

(b2, 15K)

(a3, 120K)

(b3, 120K)

Fig. 4. Surface morphology of the membranes: (a) Z, (b) Z1.

membrane Y, Fig. 3). As shown by Fig. 6(e) and (f), the peaks of the two distribution curves situated at about 56 nm and 40 nm, respectively. Moreover, Fig. 6(f) displayed the obviously narrower pore size distribution of membrane Z1, this agreed well with the

surface morphology shown in Fig. 4. Again, we attribute the higher pepsin retention of membrane Z1 (compared with membrane Z, Fig. 3) to the smaller peak pore size and narrower pore size distribution.

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Sponge structure

Upmost part of cross-section

a1

b1

c1

d1

Fig. 5. SEM photos of the sponge structure and upmost part of membrane cross-section: (a) X, (b) X1, (c) Y1, (d) Z1.

At last, two issues regarding the results of pore size distribution determined by the N2 adsorptiondesorption method need to be addressed. First, why membrane with pore size ranging from 20 to 100 nm (Fig. 6) can reject pepsin (about 5 nm in size)? Second, the

BET data in Fig. 6 have different scales, will this inuence the comparison? As for the rst one, we think it is better to seek the correlation between the solute rejection and the measured pore size, than to

Z. Wang et al. / Desalination 278 (2011) 141149 Table 2 The SBET, VBJH, and DBJH of membranes. Membrane ID X X1 Y Y1 Z Z1 SBET (m2/g) 16.8 41.2 23.4 40.7 16.0 40.1 VBJH (cm3/g) 0.075 0.296 0.256 2.365 0.269 0.306 DBJH (nm) 15.1 24.6 39.2 51.1 46.6 23.4

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judge rejection just based on the size relation. Our proposed explanation was given below: 1. The porous system would certainly have some tortuosity, the separation effect of the membrane depends on the bulk structure of the whole selective layer. 2. There is an interaction between solutes and pores, thus, ltration media sometimes could really reject particles that are smaller than their pore size. 3. For the nitrogen adsorptiondesorption method, pores in the sublayer of membrane were also measured, therefore, it gave pore sizes larger than those in the selective layer which are responsible for separation.

a
dV/dlog(D) (cm3g-1nm-1)
0.06

b
0.30

dV/dlog(D) (cm3g-1nm-1)
0 20 40 60 80 100

0.24 0.18 0.12 0.06

0.04

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Pore Diameter (nm)

c
0.20

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5.00

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dV/dlog(D) (cm3g-1nm-1)
0 20 40 60 80 100

0.15

4.00 3.00 2.00 1.00 0.00

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0.05

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Pore Diameter (nm)

e
0.25

f
0.25

dV/dlog(D) (cm3g-1nm-1)

dV/dlog(D) (cm3g-1nm-1)
0 20 40 60 80 100

0.20 0.15 0.10 0.05 0.00

0.20 0.15 0.10 0.05 0.00

20

40

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Pore Diameter (nm)

Pore Diameter (nm)

Fig. 6. Pore size distributions determined by the BJH approach from the desorption branches of N2 adsorptiondesorption isotherms: (a) X, (b) X1, (c) Y, (d) Y1, (e) Z, (f) Z1.

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Table 3 A comparison on the ux and rejection property of the present pure sponge-like membranes and some commercial PVDF membranes. Membrane ID 1 2 3 4 5 6 7 X1c Y1 Z1
a b b

Pure water ux (LMHa, 0.1 MPa) 142.8 41.6 115.9 215.2 210.2 124.8 37.4 189.4 222.1 217.1

Rejection (%) Trypsin (23 K) 59.8 55.9 66.1 18.9 35.2 36.8 31.4 57.7 61.2 61.4 Pepsin (35 K) 74.6 68.1 80.2 67.7 54.2 60.2 82.7 85.0 76.3 82.3 BSA (68 K) 99.1 60.7 98.9 98.1 48.1 89.6 96.7 95.1 89.3 92.6

Information provided by manufacturers Flux (LMH, 0.1 MPa, 25 C) 150 120 220 270 200300 150 225 MWCO (Da) 50 K 150 K 50 K 100 K 110 K 110 K 30 K Membrane type Flat sheet Hollow ber Flat sheet Flat sheet Hollow ber Hollow ber Flat sheet

Lm2 h1. Membranes 17 were supplied by GE Osmonics, Koch Membrane, Litree Company, Tianjin Motimo Membrane Technology Ltd., Shandong Zhaojin Motian Co. Ltd. c Membranes X1Z1 in this table were casted with room temperature 20 1 C, relative humidity 50%65%, other factors and procedures were same with that in preparing membranes X1Z1 in Figs. 2 and 3.

As for the second one, because the value of y-axes was calculated by dV/dlogD, so the different scales were caused by the different specic pore volumes of the six membranes as displayed by the VBJH values in Table 2, thus the comparison on pore size distribution of two membranes in each pair would not be inuenced by that. In fact, this phenomena can be frequently observed in literature [17,29,30]. 3.4. Performance comparison between the present pure sponge-like membranes and some commercial PVDF membranes Although the pure sponge-like membranes in this work displayed special characteristics in terms of their formation and properties compared with those in literature, they are valuable only if they have improved (or at least comparable) performance to existing PVDF membranes. Thus, a comparison study on the ux and rejection property of them and some commercial PVDF membranes was carried out, and the results were shown in Table 3. As can be found in Table 3, membrane X1Z1 have obviously higher ux than many commercial PVDF membranes. Though the commercial membrane 5 has relatively high ux, its rejection on trypsin, pepsin, and BSA all are quite lower than that of membrane X1Z1 (the reason for why membrane 5 showed a lower BSA rejection than pepsin rejection is not very clear, this phenomena also can be found on membrane 2). While for membrane 4, it also has high ux, however, its rejection on trypsin and pepsin both are distinctly lower than that of membrane X1Z1. Strangely, membrane 4 showed a higher BSA rejection than that of membrane X1Z1. In sum, the data in Table 3 indicate that the pure sponge-like membranes (X1Z1) achieved a good balance between the permeability and retention capacity, they showed comparable performance to the commercial PVDF membranes and even better than some of them. 4. Conclusions PVDF membrane with macrovoid structure can be prepared using ferrous chloride or calcium chloride as additive by the phase inversion method. While, pure sponge-like PVDF membrane can be prepared using a composite additive, such as ferrous chloride/nano-silica, calcium chloride/nano-silica, or ferrous chloride/hydroxylamine hydrochloride. The obtained pure sponge-like membranes all exhibit obviously higher water permeability and higher or little lower retention capacity compared with their counterpart macrovoids dominated membranes. High magnication SEM observation indicated that the sponge structures of membrane X1, Y1, and Z1 are very loose, thus should be much more permeable than the traditional sponge structure. The specic area, pore volume, and pore size distribution, measured using the nitrogen adsorptiondesorption

method, indicated that the pure sponge-like membranes (X1, Y1, and Z1) are more porous and hold narrower (X1 and Z1) pore size distributions compared with their counterpart membranes. The trends revealed by the BET data agreed relatively well with the ux and retention data, thus implied that the N2 adsorptiondesorption method might be an effective means to investigate the pore structure of polymeric membranes. The comparison study indicates that the pure sponge-like membranes in this work have comparable and even better performance characteristics than some of the existing commercial PVDF membranes in terms of ux and retention. Acknowledgements The supports from the National Natural Science Foundation of China are greatly appreciated (projects' numbers: 50778049, 50978067). References
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