1-s2.0-S0011916411004346-main | Membrane | Adsorption

Desalination 278 (2011) 141–149

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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 fluoride) (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 magnification SEM (scanning electron microscopy) photos revealed the great differences between the two kinds of macroscopically similar sponge structures. The specific area (BET surface area), pore volume, and pore size distribution, measured using the nitrogen adsorption–desorption 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 flux and retention data, thus implied that the N2 adsorption–desorption method might be an effective means to investigate the structure–property 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 flux 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 fluoride) (PVDF) Membrane preparation Sponge Macrovoid Nitrogen adsorption–desorption

1. Introduction Improving both the permeability and retention capacity of membranes for liquid separation such as drinking water purification always is a subject matter of membrane preparation [1,2]. In 1959, the first 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 permeation–retention properties. According to most of the previous researches, membranes dominated by the macrovoid structure always are more permeable than those sponge ones [4–8]. So far, various methods have been explored to generate a proper macrovoid sublayer, especially for those low-pressure membranes such as the ultrafiltration and microfiltration membranes [4–14]. 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 influencing 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 solvent–nonsolvent mutual diffusion in the immersion–precipitation process is very fast, it would benefit 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 solidification of the surface layer [21–24]. 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 flat sheet poly(vinylidene fluoride) (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

DongWu Bio-Chemical Products Company in Su Zhou. Ltd. Pepsin (Mw = 35. 2. After that. Ferrous chloride. Ltd. respectively.3.000 g/mol) used in the retention experiment were purchased from Beijing Solarbio Science & Technology Co. The wet membrane sheets were cut into circles of 31. Phillip's SEM model FEI. DMAc. Analytical reagent). the dry membrane samples were immersed in liquid nitrogen and carefully fractured which would give a generally clean break (for cross-section observation). Analytical reagent) were used as the salt additives. Analytical reagent) and distilled water (H2O) were used as solvent and coagulant respectively. 1. After Table 1 The compositions of different dope solutions (weight proportion) and their viscosity at 40 °C. respectively. Pure water flux test Pure water fluxes of the membranes were determined using a membrane testing unit (Shanghai Mosu Scientific Equipment Co. The percentage rejection (R) can be calculated according to the formula: Rð%Þ = 1−Cp = Cf where Cf and Cp denote the protein concentration in the feed and permeate respectively.4.95 m/s for the hollow fiber membranes).3. the specimens including those for surface observation were fixed on a metal support and sputtered a layer of gold with proper thickness under vacuum. obtained from Shanghai 3 F New Materials Co.5 34 N 100 29 32. and Sinopharm Chemical Reagent Co. The homogeneous solutions were uniformly cast on the glass plates with a home-made glass knife at room temperature (15 ± 1 °C). All the materials were used as received. Tianjin Bodi Chemicals Co. Ltd.4–1. Accordingly. Materials Poly(vinylidene fluoride). 18 °C) was fed into the testing unit.142 Z. the increase of dope viscosity would accordingly increase the resistance of solvent–nonsolvent mutual diffusion in the immersion–precipitation process. The subsequently detached films were removed into another distilled water container and kept for 3 days to remove the residual solvent.000 g/mol). Then certain areas of each membrane were taken out and subjected to the pure water flux test and pepsin retention measurement.g. and was driven through the membrane under 0. Tianjin Bodi Chemicals Co. and a relatively steady protein concentration of the permeate was used to calculate the rejection.2. CaCl2·2H2O. The possible explanation for the formation of pure sponge structure is given below. SBET) and pore size distribution of the membrane samples were measured using the nitrogen adsorption–desorption method on an ASAP 2020V3.000 g/mol). the out-diffusion ..1. Ltd. Wang et al. Mn = 475. 2. All the reported flux and retention values were expressed by the average of three sample measurements for each casting condition.1 MPa for 15 min. Then the feed solution was vigorously stirred (360 r/min for the flat sheet membranes while 0.. calcium chloride (FeCl2·4H2O. after the measurement of pure water flux.3. The addition of additive2 (e. 2. with the left membranes immersed into ethanol for 12 h. Experimental 2. Thus.3. Firstly.2. Netherlands). Shimadzu) at 280 nm.. NH2OH·HCl) increased the viscosity of dope solution (Table 1) [26].9 dL/g) was used as the membrane material. the macrovoid structure formation was suppressed [23]. then the trans-membrane pressure was restored to 0. The SBET was determined from the linear part of the BET curve. with their compositions and viscosities at 40 °C shown in Table 1. and BSA (Mw = 68. Membrane ID X X1 Y Y1 Z Z1 PVDF 18 18 18 18 19 19 DMAc 78 74 78 74 77 77 Additive1 4(FeCl2·4H2O) 4(FeCl2·4H2O) 4(CaCl2·2H2O) 4(CaCl2·2H2O) 2(FeCl2·4H2O) 2(FeCl2·4H2O) Additive2 0 4(SiO2) 0 4(SiO2) 0 2(NH2OH·HCl) Dope viscosity (Pa·s) 22. expectably. 2. Trypin (Mw = 23.5 that the membrane morphology were examined using a scanning electron microscope (SEM. after 20 min of distilled water (18 °C) permeation the flux was practically constant. Ltd. Membrane characterization 2. Ltd.1. nano-SiO2. The dry membranes would undergo SEM analysis and N2 adsorption– desorption experiment for the Brunauer–Emmett–Teller (BET) surface area analysis and Barrett–Joyner–Halenda (BJH) pore size distribution analysis.5 mm in diameter and subsequently installed into the testing unit. After 20 s evaporation in the air (Relative humidity ranged from 20% to 45%). 2. the sample was collected. the small increase of dope viscosity seems not the only reason for the formation of sponge-like structure. BET analysis The specific area (BET surface area.N-dimethylacetamide (DMAc. 3. / Desalination 278 (2011) 141–149 permeability and high retention capacity simultaneously have been seldom reported.2 MPa (supplied by nitrogen gas). and hydroxylamine hydrochloride (NH2OH·HCl. 1(c)–(d) and (e)–(f). the addition of hydroxylamine hydrochloride in casting solution would reduce the chemical potential thus the activity of solvent.5 66. Nano-silica (size: 20–40 nm. 1(a) and (b). the pore size distribution was calculated from the desorption branch of N2 adsorption–desorption isotherms using the BJH approach.) was used to dope the casting solution. they were immediately immersed into the distilled water (25 °C). however. Protein concentration was determined by a UV–visible spectrophotometer (UV-2550. N. protein solution (200 ppm. Tianjin Chemical Reagent Company. Additional possible reasons should be taken into account.3. and additive (s) were prepared. Similar changes of structure can be observed from membrane Y– Y1 and Z–Z1 as shown by Fig. On one hand. [η] = 1. Membrane preparation The membranes were prepared using the phase inversion method..1 MPa after which 1-min permeate was collected to calculate the pure water flux. Results and discussion 3.. 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).3. the trans-membrane pressure was set at 0. are very meaningful. obtained from Zibo Haina High Technology Co. After that. Scanning electron microscopy (SEM) analysis Firstly.70–0. China). While for membrane Z1.00H apparatus. hydroxyls on the silica surface make it hydrophilic. (FR904. Sirion 200. Then. N99%.1. Protein retention measurement For one piece of membrane sample. All the samples were degassed at 65 °C for 8 h prior to the measurement. the membranes were dried in air. Ltd. As shown by Fig.. Morphology of the membranes The cross-section morphologies of the membranes were presented in Fig.637.. 2. Dope solutions with different contents of PVDF.

respectively. 2. of solvent will be suppressed. and Z1 exhibit obviously higher pure water flux than their counterpart macrovoids dominated membrane X. (e) Z. Wang et al. In fact.2. Fig. the higher pepsin retention of membrane Z1 than that of membrane Z is consistent with the SEM photos shown in . membrane X1. Y1. and Z.Z. Pure water flux and pepsin retention of the membranes As shown in Fig. In addition to the higher pure water flux. Y1. (b) X1. On the other hand. Y. (d) Y1. its formation will not only suppress the in-diffusion of nonsolvent but also decrease the thermodynamic stability of the casting solution. hydroxylamine hydrochloride as a strong reductant might be oxidized in the dissolving process (the mixture container was not strictly sealed at this stage). 1. (f) Z1. 3. Cross-section morphology of the membranes: (a) X. Water will be generated in oxidizing hydroxylamine hydrochloride. / Desalination 278 (2011) 141–149 143 a b c d e f Fig. (c) Y. 3 showed that membrane X1. All these behaviors would suppress the formation of macrovoid structure and benefit the formation of sponge-like structure. and Z1 also bear higher or little lower pepsin retention compared with their counterpart membranes.

the N2 adsorption–desorption method measured the pore size distribution of the entire sample. 2. The obviously higher pure water flux and denser surface layer of membrane X1. / Desalination 278 (2011) 141–149 240 200 160 120 80 40 0 X X1 Y Y1 Z Z1 Membrane ID Fig.700 nm and 300. it can be found that the cellular pores of these three sponge structures all are very interconnected. the pure water flux depends largely on the surface structure and bulk structure of the membrane. Y1. 6(a) and (b) showed that the peaks of the two distribution curves both situated at about 37 nm. and Z1 were shown in Fig. 4. 5(b1). and Z. which was composed of many cellular pores. were not shown here). Similarly. structures seems related to a nucleation and growth mechanism [27. 3. respectively. Z1 53. Since the surface pore size of ultrafiltration membrane is always less than 100 nm. 2 that the larger the average pore size. VBJH). Y1. VBJH value also reflects porosity. which indicated that the surface structure comparisons of membrane X–X1 and Y–Y1 are similar to that of membrane Z–Z1. this may also contribute to the higher flux of membrane X1. The BET surface area (SBET). X1. In this context.000 nm in diameter. Fig. membrane Z–Z1 again showed an exception. Moreover. the N2 adsorption–desorption method was employed. Moreover. respectively) imply that it is more reasonable to attribute the flux difference of these membranes to their structures. . and Z. Y1.28]. 6 only displayed the distribution of those pores less than 100 nm in size. Table 2 shows that each SBET value of the sponge-like membranes is obviously higher than that of its counterpart membrane. Y1.5 μm. and (d1)) are more porous than that of membrane X (Fig. X1 57. 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. in theory. and Z1. which have been discussed above. The formation of such permeable sponge Pure water flux (Lm-2h-1) Rejection (pepsin 35K. the distribution curve of membrane Y1 is broader than that of membrane Y. 5. 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). However. Though. Though the lower thickness of membrane Z1 would contribute to its higher flux (compared with membrane Z).2 μm. We believe it was this kind of special sponge structure that made membrane X1. Though some differences also existed among the sponge structures of membrane X1.7 μm. (a3) and (b3)) of the two membranes are nearly same dense (other SEM photos. Y1. (c1). and related to the suppressed solvent–nonsolvent mutual diffusion in terms of kinetics.8 μm. 5(a) displayed the very traditional sponge structure. however. Each value was the average of five different position SEM measurements) also would influence the flux. we try to seek useful information from the pore size distribution curves and attempt to correlate them with the pepsin retention data. Generally. 5(a). respectively. 5(a1)). Fig. and BJH Desorption average pore diameter (DBJH) of the membranes were shown in Table 2. Y1. Pepsin retention of the membranes. 5 (the sponge structures of membrane Y and Z are quite similar to that of membrane X. those pores were isolated with many dense walls if not totally closed. respectively. the higher the membrane flux. and Z1. 6. 3) to the similar peak pore size of the two membranes while narrower pore size distribution of membrane X1. Fig.2 μm. Z 59. In addition to structure. the higher thicknesses of membrane X1 and Y1 and their obvious higher flux (compared with membrane X and Y. X1. and Z1 (Fig. so we prefer to try to correlate DBJH values with flux rather than with retention. It seems reasonable to attribute the higher pepsin retention of membrane X1 (Fig. a relatively good correlation can be found between the flux data (Fig. Wang et al.8 μm. Fig. even having no obvious isolating walls. since the obtained values are the average of entire pores but not just those in surface layer. Y. 3. each VBJH value of membrane X1. 6(c) and (d) showed that the peaks of the two distribution curves situated at about 45 nm and 55 nm. A systematic study on the formation mechanism will be carried out in our subsequent work. so they were not shown here). 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 structure–property relationship observed in this work. this kind of structure would be highly resistant [4–6]. in Table 2. In order to make a test for this speculation. BJH Desorption cumulative volume of pores (between 1. compared with membrane X. Y 52. however. and more porous structure might be more permeable. the higher SBET value implies a more porous structure. implied that the sponge structure of the former three membranes should be more permeable than that of the latter three ones. In this work. Pure water flux of the membranes. respectively. 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. %) 90 80 70 60 X X1 Y Y1 Z Z1 Membrane ID Fig. (b)–(d) displayed the quite different sponge structures. the upmost parts of membrane cross-sections (X. the thickness of membranes (X 57. Compared with Fig. and Z1.3. 2) and the SBET values (Table 2). Z1) were also shown in Fig. Y1. the SEM photos of the sponge structures and upmost part of cross-sections of membrane X. the pore size distributions were presented in Fig. whether or to what extent this method can reflect the real information on the surface pore structure still lacks a solid conclusion. and Z1 more permeable than membrane X. It seems that the very parts beneath the surface layer of membrane X1. As for DBJH. the pore size distribution of membrane X1 is obviously narrower. In general. Y. 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). Y1. Y1 73. It can be found from Table 2 and Fig.144 Z. In general.

/ Desalination 278 (2011) 141–149 145 Membrane Z Membrane Z1 (a1. respectively. Surface morphology of the membranes: (a) Z. Again. . Fig. ×15K) (a3. ×5K) (a2.Z. membrane Y. 4. 4. As shown by Fig. 3) to the smaller peak pore size and narrower pore size distribution. Fig. the peaks of the two distribution curves situated at about 56 nm and 40 nm. we attribute the higher pepsin retention of membrane Z1 (compared with membrane Z. ×120K) Fig. ×5K) (b1. Moreover. this agreed well with the surface morphology shown in Fig. Wang et al. Fig. ×15K) (b2. ×120K) (b3. 6(f) displayed the obviously narrower pore size distribution of membrane Z1. (b) Z1. 6(e) and (f). 3).

(b) X1. (d) Z1. why membrane with pore size ranging from 20 to 100 nm (Fig. than to . SEM photos of the sponge structure and upmost part of membrane cross-section: (a) X. First. At last. / Desalination 278 (2011) 141–149 Sponge structure Upmost part of cross-section a a1 b b1 c c1 d d1 Fig. (c) Y1. will this influence the comparison? As for the first one. Wang et al. two issues regarding the results of pore size distribution determined by the N2 adsorption–desorption method need to be addressed. we think it is better to seek the correlation between the solute rejection and the measured pore size. 6) can reject pepsin (about 5 nm in size)? Second. the BET data in Fig. 5. 6 have different scales.146 Z.

6.10 0.8 41. (d) Y1.00 0.10 0.06 b 0.00 0 20 40 60 80 100 Pore Diameter (nm) Pore Diameter (nm) c 0.05 0. Our proposed explanation was given below: 1.1 24. For the nitrogen adsorption–desorption method. (f) Z1.18 0. (e) Z.12 0.10 0.00 0 20 40 60 80 100 Pore Diameter (nm) Pore Diameter (nm) e 0. VBJH.25 f 0.30 dV/dlog(D) (cm3g-1nm-1) 0 20 40 60 80 100 0.15 4.256 2.00 0. thus.00 0 20 40 60 80 100 Pore Diameter (nm) Pore Diameter (nm) Fig. (c) Y.365 0. pores in the sublayer of membrane were also measured.06 0.02 0. .2 51.15 0.075 0.25 dV/dlog(D) (cm3g-1nm-1) dV/dlog(D) (cm3g-1nm-1) 0 20 40 60 80 100 0.Z. There is an interaction between solutes and pores.1 46. filtration media sometimes could really reject particles that are smaller than their pore size.05 0.20 0. (b) X1.20 d 5. Membrane ID X X1 Y Y1 Z Z1 SBET (m2/g) 16.6 39. The porous system would certainly have some tortuosity.05 0.00 0. it gave pore sizes larger than those in the selective layer which are responsible for separation. and DBJH of membranes.00 0.296 0. Pore size distributions determined by the BJH approach from the desorption branches of N2 adsorption–desorption isotherms: (a) X.15 0.4 147 judge rejection just based on the size relation.1 VBJH (cm3/g) 0. 3. / Desalination 278 (2011) 141–149 Table 2 The SBET. 2.2 23.269 0.306 DBJH (nm) 15. a dV/dlog(D) (cm3g-1nm-1) 0.00 3.04 0.20 0.7 16. therefore.00 2.00 dV/dlog(D) (cm3g-1nm-1) dV/dlog(D) (cm3g-1nm-1) 0 20 40 60 80 100 0.0 40.00 1. Wang et al.24 0.6 23. the separation effect of the membrane depends on the bulk structure of the whole selective layer.4 40.

Koch Membrane. they showed comparable performance to the commercial PVDF membranes and even better than some of them. 50978067). Huang. 4.M. pore volume. Membrane ID 1 2 3 4 5 6 7 X1c Y1 Z1 a b b Pure water flux (LMHa. indicated that the pure sponge-like membranes (X1.1 Rejection (%) Trypsin (23 K) 59.6 68. Li. Appl. Science and technology for water purification in the coming decades.H. J.4 Pepsin (35 K) 74. S.Z. Mehta. Membr. Sci. Zydney. J.H. Wang.30]. 163 (1999) 211–220.8 55. Desalination 104 (1996) 1–11. pure sponge-like PVDF membrane can be prepared using a composite additive. Sci. Won. Y1. Vol. Lin. J. [4] D. [8] M. ACS symposium series 153.6 Information provided by manufacturers Flux (LMH. Membr. The specific area. A. In fact. Shannon.J. K. Membr.P. Sci. B. Synthetic Membrane. J. S. 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. Koo.W. Preparation and characterization of polyacrylonitrile ultrafiltration membranes. Membr. Nature 452 (2008) 301–310. S.. Preparation and properties of flat-sheet membranes from poly (vinylidene fluoride) for membrane distillation. H. W. other factors and procedures were same with that in preparing membranes X1–Z1 in Figs. measured using the nitrogen adsorption–desorption method.2 210. 60 (1996) 1343–1348. References [1] A. thus the comparison on pore size distribution of two membranes in each pair would not be influenced by that. M. T. High performance ultrafiltration membranes cast from LiCl doped solutions. I.A. Conclusions PVDF membrane with macrovoid structure can be prepared using ferrous chloride or calcium chloride as additive by the phase inversion method. Van den Boomgaard. thus should be much more permeable than the traditional sponge structure. Shandong Zhaojin Motian Co. Porous PVDF asymmetric hollow fiber membranes prepared with the use of small molecular additives. Phase behavior and morphological studies of polyimide/PVP/solvent/water systems by phase inversion. Effect of salt additive on the formation of microporous poly(vinylidene fluoride) membranes by phase inversion from LiClO4/Water/DMF/PVDF system. 249 (2005) 245–249. Georgiadis.6 115.1 60.M. A.1 18.1 MPa.P. membrane 4 showed a higher BSA rejection than that of membrane X1–Z1. Smolders. K.3 92. Sci. and Z1) are more porous and hold narrower (X1 and Z1) pore size distributions compared with their counterpart membranes. calcium chloride/nano-silica. Membranes 1–7 were supplied by GE Osmonics. Membr. [14] J. 3. [12] J. Thus. The role of a polymeric additive.L. Polymer 44 (2003) 413–422. they are valuable only if they have improved (or at least comparable) performance to existing PVDF 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 flux and retention. Li.1 MPa) 142. 2 and 3. however. [9] D. Strangely. pepsin. the data in Table 3 indicate that the pure sponge-like membranes (X1–Z1) achieved a good balance between the permeability and retention capacity. [15] D.7 61. W.C.4 222. Bottino. Sci. [13] R. Higuchi. While.J.9 35. Capannelli.J. Desalination 68 (1988) 167–177.L.T.H.2 61. this phenomena can be frequently observed in literature [17. Sci. such as ferrous chloride/nano-silica. C. . 138 (1998) 153–163. Deshmukh. [6] A. C. In sum. Wang. TurbakA F. its rejection on trypsin.0 76. 150 (1998) 75–85.S. Boom. Bohn.1 89. P. Lee. While for membrane 4.7 54. c Membranes X1–Z1 in this table were casted with room temperature 20 ± 1 °C. J. Hwang. / Desalination 278 (2011) 141–149 Table 3 A comparison on the flux and rejection property of the present pure sponge-like membranes and some commercial PVDF membranes.9 215. As can be found in Table 3. J. B. Li. K. Part 2. Effect of PEG additive on membrane formation by phase inversion. As for the second one. 222 (2003) 87–98. Litree Company. Wienk.2 124. J. High magnification SEM observation indicated that the sponge structures of membrane X1.9 66.3 BSA (68 K) 99. so the different scales were caused by the different specific pore volumes of the six membranes as displayed by the VBJH values in Table 2. F. Sci. Kim. Microstructures in phase inversion membranes. Sci. Acknowledgements The supports from the National Natural Science Foundation of China are greatly appreciated (projects' numbers: 50778049. Nam.1 48. T. 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. Membr.2 60. Marinas. J. [2] M. Turturro. Tianjin Motimo Membrane Technology Ltd. [5] S. [11] S.R.7 85.4 189.4 57. Loeb.L. and BSA all are quite lower than that of membrane X1–Z1 (the reason for why membrane 5 showed a lower BSA rejection than pepsin rejection is not very clear. Yang. 1. Teo. 25 °C) 150 120 220 270 200–300 150 225 MWCO (Da) 50 K 150 K 50 K 100 K 110 K 110 K 30 K Membrane type Flat sheet Hollow fiber Flat sheet Flat sheet Hollow fiber Hollow fiber Flat sheet Lm−2 h−1.4.M.R.6 96. Y. Elimelech. and Z1 are very loose. and the results were shown in Table 3.8 31.1 217. because the value of y-axes was calculated by dV/dlogD. Y1. Teo. relative humidity 50%–65%.K.1 80. Ltd. The Loeb–Sourirajan membrane: how it came about. Polym. Liu. Sci.A. 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