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Journal of Membrane Science 302 (2007) 7886

Organicinorganic composite pervaporation membranes prepared by self-assembly of polyelectrolyte multilayers on macroporous ceramic supports
Yiwei Chen, Fenjuan Xiangli, Wanqin Jin , Nanping Xu
Membrane Science and Technology Research Center, State Key Laboratory of Material-Oriented Chemical Engineering, Nanjing University of Technology, Xinmofan Road 5, Nanjing 210009, PR China Received 21 March 2007; received in revised form 10 June 2007; accepted 12 June 2007 Available online 15 June 2007

Abstract An organicinorganic composite membrane was successfully prepared by means of electrostatic self-assembly of polyelectrolytes on silica solgel modified macroporous ceramic supports. The integrality of the as-prepared composite membrane was evaluated in pervaporation of ethanol/water mixtures. Membrane separation performance was optimized by studying the modification cycle, polyelectrolyte molecule structure, self-assemble conditions, thermal treatment conditions and operating temperatures. It was found that the polyelectrolyte molecule structure mainly affected the separation performance of the composite membrane after a two-cycle modification and raising pervaporation operating temperature was an efficient way to improve both membrane flux and water selectivity. The composite membrane deposited by 60 layer pairs of polyethylenimine/poly(vinyl sulfate) (PEI/PVS) showed a high flux of 18.4 kg m2 h1 and a water concentration enhancement from 6.2 to 35.3 wt.%. Our study demonstrates that the composite membrane prepared on macroporous ceramic support through our route is suitable for separation of liquid species at a molecular level. 2007 Elsevier B.V. All rights reserved.
Keywords: Composite membrane; Self-assembly; Polyelectrolyte multilayers; Macroporous ceramic support; Pervaporation

1. Introduction Vast majority of the studies on polyanionpolycation complex formation were performed in the bulk solutions until a new approach developed by Decher et al. [1,2] extended the experiments by allowing study the complexes of oppositely charged polyelectrolytes assembled onto solid substrates. Such polyelectrolyte complexes, also mentioned as polyelectrolyte multilayers (PEMs), show higher structural hierarchy that can be fully exploited in the design of macroscopic devices for nonlinear optics, catalysis, microelectronics, as well as biomedicine [35]. Due to their extremely low thickness, high homogeneity and nice tunability on molecular dimensions, PEMs are attractive materials as ultrathin selective layers assembled on porous supports to obtain composite membranes for separation

Corresponding author. Tel.: +86 25 83587211; fax: +86 25 83587211. E-mail address: wqjin@njut.edu.cn (W. Jin).

of nanoscale species. One important technical factor encountered in electrostatic self-assembly on porous support is the choice of the support pore size. Though larger pore size means less flow resistance and higher flux, the difficulty in forming defect-free polyelectrolyte selective layer on such support is obvious. Since each adsorption step only adds about a few nanometers to the total thickness of the multilayers and the bridging or complexation of polyelectrolyte molecules is under nanoscale [2], the pore size of the support should be restrained within a feasible value to be well covered by PEMs [6,7]. Stroeve et al. [7] used macroporous polypropylene membranes (with 0.4 urm 0.04 urm slit-like pores) as the substrate for carrying out self-assembly of PEMs from pair of polyallylamine/polystyrenesulfate (PAH/PSS). It was shown that the PEMs formed on the untreated macroporous support were nonselective for gas permeation even after 40 coatings of the polyelectrolytes. Porous supports such as polypropylene [7], poly(4-methyl1-pentene) (PMP) [8], polyamide [9], polyacrylonitrile (PAN) [6,1016], poly(vinylpyrrolidone) (PVP) [17] and anodic alu-

0376-7388/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.memsci.2007.06.019


Y. Chen et al. / Journal of Membrane Science 302 (2007) 7886 Table 1 Supports with different pore size levels for polyelectrolyte self-assembly to prepare PV membranes reported in literature Supports Organic Carboxyl functionalized polyamide-6 (obtained by phase-inversion process) PAN, molecular weight cut-off of 20,000, pore size of about 35 nm PAN pore size of 20200 nm Anodic alumina pore size of 20 nm

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Membrane performance flux (kg m2 h1)/selectivity Waterethanol (Cw = 10 wt.%), 0.02/1400, temperature: 50 C Waterethanol (Cw = 9 wt.%), 1.8/495, temperature: 70 C Waterethanol (Cw = 6.2 wt.%), 0.047/556, temperature: 60 C Waterethanol (Cw = 10 wt.%), 1.9/500, temperature: 50 C

Reference [9] [6,10] [15] [16]

Inorganic

mina [1820] was commonly used for self-assembly of PEMs. Some pervaporation membranes fabricated by successful selfassembly of polyelectrolytes on supports with different pore size levels were listed in Table 1, as well as their separation performances. The PEMs on the oxygen plasma treated PAN supports (pore size of 20200 nm) were extensively studied by Tieke et al. [1316] and the membranes showed a good selectivity to water in pervaporation while the flux were normally under 1 kg m2 h1. PAN supports of more microporous level (molecular weight cut-off of 20,000 PEG, and the estimated pore size is about of 35 nm [21]) was selected by Feng et al. [6,10], and the PEMs deposited on the supports which have been hydrolysed in sodium hydroxide solution showed a better separation performance. Anodic alumina membrane with 20nm diameter surface pores was used by Bruening et al. [18] as supports and treated by UV/O3 cleaning before PEMs selfassembly. The as-prepared composite membrane was able to work in pervaporation, but the anodic alumina supports obtained by a special fabrication procedure had a limited potential for application. One could notice that most successful self-assembly of polyelectrolytes layers for pervaporation membranes are deposited on supports with microporous or mesoporous level. Ceramic microfiltration membranes with macropores as one kind of mature products have been commercially applied for years, the cost of which has been controlled much lower than those of the ultrafiltration or nanofiltration membranes. In our previous work [22], the poly-dimethyl siloxane (PDMS)/ceramic pervaporation membranes prepared by phase inversion of polymers on the macroporous ceramic supports (pore size, 0.2 urm) have showed exciting high flux (19.5 kg m2 h1, 70 C) for ethanol removal in water/ethanol system. For organicinorganic composite membrane, the organic top layer provides a good selectivity while the inorganic porous support favors the membrane a high flux because it restrains the deformation of organic layer, which might be considered as the effect of confined deformation. The organicinorganic composite membrane prepared from macroporous supports will be considerably promising, so is the application of electrostatic self-assembly technique on fabricating composite membranes from macroporous supports. However, few studies have been researched on the self-assembly upon the ceramic macroporous supports because of the difficulty to obtain membranes for separation of species at a molecular level.

In this paper, one new route was firstly proposed to prepare organicinorganic composite membrane for pervaporation by means of electrostatic self-assembly of polyelectrolytes on pretreated macroporous ceramic supports. A silica solgel modification was applied to tune the pore size of the macroporous ceramic supports. Subsequently, a simple cleaning process was performed to make ceramic oxide surface fully hydroxylated. Fig. 1 illustrates the procedure and the necessity of the pretreatment process. As mentioned above, direct self-assembly of the polyelectrolytes on macroporous supports without pretreatment would be incomplete since the weak adsorption of the polyelectrolyte layers cannot cover the large pores on the membrane surface. With the tuning of the pore size of macroporous supports and wet cleaning of the oxide surface, the complete self-assembly could be achieved because the enhanced electrostatic adsorption of the polyelectrolyte layers could bridge the tuned pores. The integrality of the as-prepared composite membrane was studied in the separation of ethanol/water mixtures under pervaporation conditions. We observed that the composite membrane shows a high flux in pervaporation because of its composite structure of thin top layer and non-deformable porous support layer.

Fig. 1. Schematic procedure of the composite membrane fabrication and the influence of the support pretreatment on self-assembly of polyelectrolytes.