Journal of Membrane Science 365 (2010) 225231

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Journal of Membrane Science

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

Co-sintering synthesis of bi-layer titania ultraltration membranes with intermediate layer of sol-coated nanobers
Minghui Qiu, Su Fan, Yuanyuan Cai, Yiqun Fan , Nanping Xu
State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry and Chemical Engineering, Nanjing University of Technology, Xin Mofan Road 5, Nanjing 210009, China

a r t i c l e

i n f o

a b s t r a c t
The preparation of titania ultraltration membranes with intermediate layer of sol-coated nanobers is briey described. In this process, titiania nanobers cover on the porous substrate to produce uniform layer with high porosity and ux. The use of titania nanoparticles from sol has been found to bring an improvement on the mechanical strength of the titania nanober membrane due to the formation of sintering neck between nanobers with colloidal particles (sol) at lower sintering temperature. In order to reduce the pore size and achieve high separation efciency, titania colloidal particulate sol is used to coat on the top of the titania nanober layer and then co-sintered at the suitable sintering temperature of the titania gel (480 C) to prepare ultraltration membranes. Furthermore, the coating times of titania sol are optimized based on the measurements supplied by permeation and separation performance and a delicate control of the coating times indeed plays a key role in the preparation of the defect-free membrane with high performance. In this work it is found that the prepared membrane has homogeneous surface without obvious defects in case of three coatings of titania sol co-sintered with the ber layer at 480 C. Property tests display that the pure water ux reaches 1100 L m2 h1 bar1 while the molecular weight cut-off is 32,000. 2010 Elsevier B.V. All rights reserved.

Article history: Received 31 March 2010 Received in revised form 27 July 2010 Accepted 6 September 2010 Available online 15 September 2010 Keywords: Ceramic membrane Ultraltration Sol-coated nanobers Co-sintering

1. Introduction Nanobers have attracted considerable interest due to their unique properties and potential applications in many areas [1,2]. Recently there have been some attempts to prepare microltration or ultraltration membranes from metal oxide nanobers [36]. Such nanober membranes normally have an asymmetric structure with a separation layer supported by a macroporous carrier. In these researches the separation layer is made of metal oxide nanobers with the diameter ranging from tens to hundreds of nanometers rather than common oxide particles. Ceramic membranes with a separation layer of oxide nanober expectedly not only inherit the advantage of conventional ceramic membranes such as thermal and mechanical stabilities, chemical and microbiological resistance, and long lifetime [7], but also adequately utilize the aspects of nanobers to attain high porosity and low ow resistance [8,9]. Compared with the conventional ceramic membrane prepared from oxide particles, the nanober membranes have some advantages. Firstly, the porosity in the separation layer formed from the interconnected nanobers can be over 70% to achieve higher

Corresponding author. Tel.: +86 25 83172277; fax: +86 25 83172292. E-mail address: yiqunfan@njut.edu.cn (Y. Fan). 0376-7388/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.memsci.2010.09.005

ux with similar separation performance. But conventional ceramic membranes prepared from particles always have a porosity below 36% and have some dead-end pores that make no contribution to the ux [4]. Secondly, the dip-coating technique allows nanobers to interconnect on the surface of supports, which could preclude inltration of nanobers. Thirdly, the randomly oriented nanobers have high elastic modulus and thermal stress resistance, decreasing the formation of pinholes and cracks during the drying and sintering process, and thus the sintered membranes with oxide nanobers possess high thermal shock resistance [10]. Finally, it is possible to adjust the membrane pore sizes and surface roughness by controlling the stacking density of nanobers. Therefore, construction of asymmetrical membranes with a separation layer of metal oxide nanobers should be an effective way for preparing high-performance ceramic membranes. However, the mechanical strength of nanober membranes is not sufcient for their application in a long run, especially for tubular ceramic membrane. It is necessary to enhance the interaction between bers [11]. Acid phosphate was rstly adopted as a binder to improve the strength of the alumina ber lters due to the bonding at the junctions of bers [12]. Silica or alumina sol can also be used as binders to enhance strength of ber membrane as bers can be connected by ne colloidal particles at relatively low sintering temperature, with the minimal loss of ux. Furthermore, the

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used colloidal particles and bers materials of same type have the uniformly thermal expansion [13,14]. In this work, we prepared tubular ceramic membranes with titania nanobers. They have unique features including hydrophilicity, anti-fouling [15], semi-conductivity, biocompatibility [16], and potential applications in photocatalytic membrane reactions [17]. To improve the strength of titania nanober membranes, titania sol was used to coat the surface of the nanobers to increase the bonding at the junctions of nanobers during the sintering process. Moreover, titania sol was coated repeatedly on the top of the ber layer to reduce the pore size and achieve high separation efciency. The performances of nanober membranes were characterized by measuring pure water ux and retention rate. 2. Experimental 2.1. Fabrication of titania nanober membranes Titania bers, provided by our collaborator Prof. Lus Group from Nanjing University of Technology, were synthesized by ionexchange reaction from potassium tetratitanate ber (K2 Ti4 O9 ) based on the hydrate conditions. In the hydration process, the hydrate intermediate H2 Ti4 O9 1.2H2 O were obtained when the molar ratio of Ti/K in solid phase were controlled at >20 by adjusting the pH value to 2. With further treated of intermediate at 800 C in mufe furnace for 2 h, the derivatives of anatase TiO2 nanobers were synthesized [18,19]. The resultant raw anatase TiO2 bers may contain coarse particles, removed by water scrubbing method owing to gravity settling. Titania sol was synthesized by hydrolysis of tetrabutyl orthotitanate (TBOT) supplied commercially without further purication. TBOT, anhydrous ethanol, nitric acid, deionized water and acetylacetone were mixed to give volume ratios of 25:250:0.55:5:600 at 8590 C. This mixed solution stirred for 4 h to ensure complete mixing and hydrolysis [20,21]. The pre-treated nanobers without coarse particles were dispersed into titania sol (0.75 wt%) to form suspension, in which the ratio of nanobers and nanoparticles from sol were controlled at 9:1. The deionized water was added to the suspension to adjust the solid content of titania. After stirring for 2 h, methylcellulose (MC) (SigmaAldrich Corporation, molecular weight: 40,000) was introduced into the suspension as a polymer additive and stirred for another 30 min. To achieve well-dispersion, the suspension of sol-coated nanober was further treated in ultrasonic for 10 min and nally labeled TF. The supports used were porous -alumina tubes with the dimensions of 12 mm in outer diameter, 2 mm in wall thickness, 85 mm in length and 23 m in mean pore diameter. The porosity, surface roughness and pure water ux were 35%, 2 m and 10,000 L m2 h1 bar1 , respectively. Titania nanober membranes were fabricated by a dip-coating process on the inner surface of the tubular supports. The treated support was dip-coated with TF suspension for 60 s, dried under an ambient environment for 12 h and at 80 C for 12 h, followed by sintering at 480 C for 3 h in the mufe furnace (at a heating and cooling rate of 0.5 and 1 C/min, respectively). 2.2. Preparation of ultraltration membrane supported by the nanober layer Titania ultraltration membranes were prepared by coating titania sol on the nanober layers. Fig. 1 shows the particle size distribution of titania sol measured by Mastersizer 3000 particle size analyzer (Malvern, Britain) and exhibits a monomodal distribution centered at 25 nm. Then polyvinyl alcohol (PVA) (SigmaAldrich Corporation, molecular weight: 13,00023,000) was added into the sol as a polymer additive and stirred for 30 min, followed by ultrasonic treat for 10 min. The resultant titania sol was labeled TS.

Fig. 1. Particle size distribution of titania sol (number analysis).

After coating TF on porous supports for 60 s, the wet membranes were dried at room temperature for 12 h to serve as the substrate of solgel membrane. Then the nanober layers were processed with the repeating coating procedure with TS for 60 s, followed by drying in a oven at 75 C in a relative humidity of 75% for 10 h. In order to make the defect-free top-layer, TS sol was used to coat several times and dried with the same process. At last, membranes were co-sintered in air at 480 C for 3 h in mufe furnace (at a heating and cooling rate of 0.5 and 1 C/min, respectively). 2.3. Characterization of titania membranes The viscosity of suspension TF and sol TS were measured by rotary viscosimeter (DV-II+, Brookeld Engineering Labs., Inc., USA) at 30 C. Thermogravimetric analysis for the dried powders of TF and TS were accomplished using 10 C/min heating rate (DTA/TG, Netzsch STA 409). The crystal structures of the sintered membranes were studied by X-ray diffraction (XRD; Bruker D8 Advance), using Cu K radiation with 2 from 20 to 80 . Morphologies of the prepared membranes were examined by scanning electron microscopy (SEM) (Quanta 200, FEI, Netherlands) and eld emission scanning electron microscopy (FESEM) (HITACHI S-5000). The thickness (L) of the layer was determined by the increased weight of the tubular supports after the formation of the membrane, and can be calculated by the following equation: L= W2 W1 A (1 ) (1)

where is the porosity of membrane layer, measured by Archimedes method used symmetric sample; A is the membrane area; is the titania theoretical density; W1 is the weight of support and W2 is the total weight of the support and the membrane layer. The pore size distributions of the supports and membranes were determined by the gas bubble pressure method (GBP) [22] and the liquid/liquid displacement porometry (LLDP) [23], respectively, according to the size of separation pore. The pure water ux (PWF) was determined in a tangential-ow ltration apparatus by collecting the permeation in a graduated cylinder and timing the collection period. The separation performance was analyzed by rejection molecular weight, following standard ultraltration tests with aqueous dextran solutions [24]. The feed solution contained dextrans with molecular masses of 10,000, 40,000, 70,000 and 500,000. The dextrans concentration were 2.5 g/L for 10,000, 1 g/L for 40,000, 1 g/L for 70,000 and 2 g/L for 500,000. Analysis of

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Fig. 2. The morphology of titania nanobers sintered at different temperature: (a) raw material, (b) 400 C, (c) 600 C, (d) 800 C.

the feed and permeate solutions was conducted by gel permeation chromatography (GPC, Waters). The molecular mass of dextran corresponding to 90% retention was considered as the molecular weight cut-off. 3. Results and discussion 3.1. Effect of sintering temperature on the structure of nanobers Sintering process has a signicant effect on the morphology of nanober and, consequently, on the microstructure of the nanober membrane. Fig. 2 shows the morphology of titania nanober before and after sintered at a series of temperatures. According to the SEM images present in Fig. 2(a), the raw material exhibit good aspects with a diameter of 200400 nm and a length of 510 m. When the temperature was 400 C, the morphology of nanobers maintained well (Fig. 2(b)). Once the temperature increased to 600 or 800 C (Fig. 2(c) and (d) it was difcult in construction of nanober membrane owing to the fracture and agglomeration of titania nanobers. The inuence of sintering temperature on the structure of nanobers could be attributed to the phase transformation of the TiO2 membrane from anatase to rutile, which was conrmed by XRD analysis. Fig. 3 displays the XRD patterns of the titania nanobers after calcination at temperature range of 4001000 C. The sample sintered at the temperature lower than 600 C is composed of pure anatase (JCPDS card No. 21-1272). As the temperature increases from 600 to 800 C, the anatase titania remains as the main phase, which is in good agreement with JCPDS card No. 655714. But new diffraction peaks centered at 38 corresponding to the crystal face of (0 0 4) are observed. Higher temperature causes phase transformation from anatase to rutile for titania nanobers. It has been reported that the morphology of nanober is sensitive to the phase transformation during the sintering process [25,26]. To keep nanober in anatase phase, the nanober membrane should be sintered at the temperature less than 600 C. When the nanober membrane sintered at a lower temperature, however, the less

neck growth between nanobers brings inevitable reduction of strength. 3.2. Preparation of nanober membrane sintered with the aid of sol Titania sol has a positive effect on improving the mechanical strength of nanober membrane because sintering neck between nanobers could be fabricated with colloidal particles. Fig. 4 illustrates the nanober on the supports after co-sintering with sol. The surface of nanobers is coated by titania particle sol to enhance the bonding at the junctions of nanobers. Therefore, the key factors for controlling the structure of the nanober membrane are the dispersion stability of sol-coated nanober suspension, the matching ability between nanober layer and the support, and the sintering process. Firstly, the suspension of sol-coated nanobers (TF) should be stable. The solid content and pH of the as-prepared suspensions are controlled to be 5 wt% and 3 to ensure dispersion stability of

Fig. 3. XRD patterns of sol-coated titania ber sintered at 4001000 C for 3 h.

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Fig. 7. The pure water uxes of nanober membrane before and after ultrasonic treatment.

Fig. 4. Schematic illustration of the ber sintered with the aid of sol.

aqueous suspension. The stability is judged by the change of the suspension viscosity, which remains 4 cP in 10 h. The nanober layer is formed on the porous support by dip-coating method. After coating with TF suspension, the nanobers lie randomly on the porous support with the thickness of 5 m calculated by Eq. (1), indicating sufcient thickness to cover the entire rough surface of the alumina support. The suitable sintering temperature of nanober membrane strongly depends on the sintering activity of sol because nanober could be connected by nanoparticles from sol. Fig. 5 displays the thermal evolution diagram of titania gel by the analysis of TG/DSC. It is shown that the sintering temperature for titania sol membrane lower than 400 C is not considered due to the risk of insufcient burnout of the organic additive. However, it is unreasonable for sol membrane to be sintered at higher than 500 C because of the transformation from anatase phase to rutile phase corresponding to an exothermic peak at 5001000 C in the DSC curve. Fig. 6 presents morphologies of TF membrane sintered at 480 C. It reveals that the surface has no visible pinholes and cracks, and the sol particle between bers can be observed. To achieve a better understanding of the effect of the sol in nanober membrane, the nanober membranes sintered without sol were prepared at the sintering temperature of 480 C and their strength was compared to that of the nanobers membranes sintered with the aid of sol. The pure water uxes of both membranes before and after ultrasonic treatment have been measured and displayed in the Fig. 7. The results can verify that the nanober membrane sintered with the aid of sol can withstand ultrasonic vibration (160 W, 40 kHz) for 30 min without damage. But the nanober membrane sintered without sol show unsatisfactory interfacial adherence. 3.3. Co-sintering synthesis of bilayer titania membranes The ceramic membrane with a separation layer of titania nanobers can be prepared with the aid of titania sol. To reduce the pore size and achieve high separation efciency, titania colloidal particulate sol (TS) has been coated on the top of the titania

Fig. 5. Thermogravimetry result of titania gel during sintering in air atmosphere.

Fig. 6. The surface morphology of TF membrane sintered at 480 C: (a) 10,000 and (b) 50,000.

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Fig. 8. Schematic diagram of bi-layer membrane with medium layer of sol-coated bers.

nanober layer to prepare ultraltration membranes via the solgel process. In addition, the co-sintering technique should be applied to fabricate the present ultraltration membrane because the bonding strength of the nanober layer was controlled by the neck connection between colloidal particles rather than nanobers. Fig. 8 shows the schematic diagram of bi-layer membrane from the sol-coated ber as transition layer, and titania colloidal sol as separation layer. The coating and drying steps of sol layer were usually repeated so that the membrane can be sufciently covered and crack-free [27]. Fig. 9 gives the pore size distribution of the support and nanober membrane characterized by gas bubble pressure method. It is shown that the mean pore size of the alumina support is up to 23 m (curve a in Fig. 9), and the titania nanober membrane has pores of 12 m (curve b in Fig. 9), which is in agreement with the results from morphologies of TF membrane (Fig. 6). Considering a diameter of 200400 nm of the titania ber, it is difcult to further reduce the pore size of the nanober membrane. The pore size distribution of the bi-layer titania membrane

with three coatings of titania sol was also displayed in Fig. 9 (curve c). By coating the titania sol layer, the sizes of the ltration pores could be reduced to 12 nm, to enhance selectivity of the membrane. Fig. 10 displays the morphologies of membrane with three coatings of titania sol co-sintered with the ber layer at 480 C. Fig. 10(a) and (b) reveals that the surface of top-layer membrane is homogeneous without evident defects. It is composed of titania spherical particles which can cover the surface of ber layer completely. From Fig. 10(c) it can be found that the sub layer is composed of bers and has an approximate thickness of 5 m, coinciding with the thickness calculated by weighing. And the top-layer membrane with the thickness of 800 nm exhibits uniform and excellent interface with good adherence to ber layer.

3.4. Performance of titania membranes The permeability and separation efciency of the membranes were measured by pure water ux (as shown in Fig. 11) and dextran retention test (as shown in Fig. 12), respectively. After coating with sol-coated bers, the ux of the nanober layer was close to 4000 L m2 h1 bar1 , which was approximately 30% of the ux of the porous alumina substrate, while rejection efciency of TF layer for dextran was enhanced obviously. Further coating of titania sol on the nanober layer, the top layer membranes have a higher rejection but lower ux. For solgel method, the integrity of the membrane is strongly related to the thickness, which can be controlled by the concentration of the sol. Moreover, the concentration of the sol solution has effect on the colloidal diameters [28]. The sol with the concentration of 0.75 wt% and with the colloidal diameter of 25 nm is too dilution to form adequate coating on the substrate, and thus the repeated coating process of the sol was needed to increase the membrane thickness. The results of ux and retention in Figs. 11 and 12 indicate that three coating times may be sufcient for complete coverage to form a defect-free membrane in our work. By contrast with the tubular titania/-alumina composite membrane of high (>90%) ltration efciency on BSA (66 kDa) [29,30], the present membrane in this work possess better separa-

Fig. 9. Pore size distribution of porous alumina support, nanober membrane and bi-layer titania membrane with three coatings of titania sol.

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Fig. 11. Pure water ux through TiO2 membranes, as a function of coating times of TiO2 sol, co-sintered at 480 C for 3 h.

Fig. 12. Molecular retention curves of support, titania nanober membrane and top ultraltration membrane.

Fig. 10. The SEM morphology of the bi-layer TiO2 membrane co-sintered at 480 C. (a) Surface image 10,000; (b) surface image 180,000; (c) cross-section image.

tion efciency with MWCO of 32 kDa while maintaining a high ux of 1000 L m2 h1 bar1 . Based on the correlation between the molecular radius (a) and molar mass (M) (a = 0.33M0.46 ), the diameter of dextran corresponding to the cut-off of molecular weight (32 kDa) is calculated to 8 nm, which is a litter less than the pore size of the membrane determined by the liquid/liquid displacement porometry. It is reasonable that the dextran molecule with smaller size than ltration pore could be rejected due to the deposition and adsorption of dextran on the membrane surface and within the pores. Further increasing thickness by more number of coatings tends to crack easily when being dried or sintered and, hence, rejection decrease. When the coating times of sol are more than three, the ux increases while the separation efciency for dextran lower down. The reason is that the present ultraltration membranes were prepared by repeated coating and drying procedure, fol-

Fig. 13. The surface morphology of bi-layer TiO2 membrane after vefold cycle of sol.

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lowed by the co-sintering process, not via conventional method of multiple sintering cycles. Although the thickness of each layer is sufciently thin to decrease the risk of crack-formation during drying period, many cracks and defects occurred after vefold cycle followed by one step sintering process, which can be clearly seen in Fig. 13. 4. Conclusions Titania nanobers are used to construct separation layer on porous supports. The sintering temperature is investigated by the analysis of TG/DSC, XRD and SEM characterization. It is shown that nanober should be sintered at the temperature lower than 600 C in order to prevent phase transformation and keep nanober morphology. Titania sol has a positive effect on improving the mechanical strength of nanober membrane because sintering neck between nanobers could be fabricated with colloidal particles. Therefore, the nanober membrane can be sintered at 480 C with the aid of sol. In order to reduce the pore size and achieve high separation efciency, titania colloidal particulate sol has been coated on the top of the titania nanober layer to prepare ultraltration membranes via the solgel process. Both layers can be co-sintered at 480 C which is the suitable sintering temperature of the titania gel. Furthermore, the coating times of titian sol are optimized based on the measurements supplied by permeation and separation performance. The results show that three coating times should be sufcient for complete coverage to form a defectfree membrane. When the membrane with three coatings of titania sol co-sintered with the ber layer at 480 C, the prepared membrane has homogeneous surface without obvious defects. And the pure water ux reached 1100 L m2 h1 bar1 while the molecular weight cut-off is 32,000. Acknowledgements This work was supported by the National Basic Research Program of China (no. 2009CB623400), the National High Technology Research and Development Program of China (no. 2007AA030303 and no. 2009AA033005) and the National Nature Science Foundation of China (no. 20636020). We sincerely thank Prof. Xiaohua Lu from Nanjing University of Technology for providing highperformance titania nanobers. And we also thank Dr. Xuebin Ke from Queensland University of Technology for his helpful discussion. References
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